Polyorganosiloxane Demulsifier Compositions and Methods of Making Same

ABSTRACT

The invention relates to a method for separating emulsions of oil and water, the method comprising incorporating a demulsifying-effective amount of a polyorganosiloxane demulsifier into an emulsion comprising an oil phase and an aqueous phase. The invention also relates to compositions containing polyorganosiloxane demulsifier and the water and oil phases of an emulsion.

FIELD OF THE INVENTION

The invention relates to polyorganosiloxane demulsifiers of particularuse in separating water emulsified in oil.

BACKGROUND

Demulsifying agents break emulsions and/or mixtures of polar soluteslike water, and non-polar solvents like oil. They are used in functionalfluids (such as, but not limited to, metal removal fluids, greases, rustand oxidation fluids, hydraulic oils, compressor oils, fuels andtransformer fluids) to inhibit formation of emulsions, break emulsionsthat have developed, and to inhibit corrosion.

Emulsions and mixtures can be separated by various means includingmechanical, thermal, and chemical. The mechanical separation of mixturescan generally result in the at least partial separation of aqueousand/or oil phases that may be present in the mixture, but when thesephases are present in the form of an emulsion, mechanical separationoften fails to provide a desirable degree of separation. Variouschemical means have been provided for separation of emulsified phasemixtures, but various industries require stilt further levels ofseparation that here to fore have not been adequately provided byconventional chemical means.

Among their industrial uses, demulsifiers are commonly used to dehydrateand desalt crude oil during extraction or refinement. Typically, duringproduction of crude oil, water gets emulsified to it to give awater-in-oil emulsion. This water-in-oil emulsion gives rise to severaldown stream problems; corrosion during refinery processes and greaterenergy requirement to pump the more viscous emulsion are to name a few.Thus, demulsifiers are extensively used in oil field applications tobreak water in crude oil emulsions.

Other industrial uses include hydraulic systems wherein the demulsifiersmust be effective at high temperatures, often in excess of 300° C.Failure of a demulsifier in a hydraulic system may lead to catastrophicfailure. Demulsifiers are also frequently put to use in hydraulicsystems to prevent corrosion. In the presumed mechanism of corrosioninhibition, the demulsifier adsorbs on the metal surface forming aprotective film against polar solutes.

Demulsifiers are known in the art and usually comprise blends of surfaceactive chemicals and the spectrum of usable compounds has been expandedparticularly due to the introduction of specific organic siliconecompounds for breaking petroleum emulsions. However, despite the largenumber of demulsifiers available on the market, it is not possible tobreak all of the occurring petroleum/water emulsions rapidly, safely,efficiently, and with small quantities of addition products.

There remains a need for demulsifiers capable of breaking and/orseparating such emulsions more effectively.

SUMMARY OF THE INVENTION

These and other objectives have been achieved by providing a method forseparating emulsions of oil and water, the method comprisingincorporating a demulsifying-effective amount of at least onepolyorganosiloxane demulsifier into an emulsion comprising an oil phaseand an aqueous phase, the polyorganosiloxane demulsifier having amolecular structure comprising a polysiloxane backbone of at least twosiloxane units covalently bound to (i) one or more pendant alkyleneoxide groups comprising one or more alkylene oxide units independentlyhaving 1 to 6 carbon atoms, (ii) one or more pendant groups having theformula (C_(r)H_(2r))B wherein r equals 0 to 30 and B is an arylradical, and optionally (iii) one or more pendant alkyl groups with upto 40 carbon atoms.

In another aspect, the invention relates to a composition comprising:

-   -   a) a demulsifying-effective amount of at least one        polyorganosiloxane demulsifier having a molecular structure        comprising a polysiloxane backbone of at least two siloxane        units covalently bound to (i) one or more pendant alkylene oxide        groups comprising one or more alkylene oxide units independently        having 1 to 6 carbon atoms, (ii) one or more pendant groups        having the formula (C_(r)H_(2r))B wherein r equals 0-30 and B is        an aryl radical; and optionally (iii) one or more pendant alkyl        groups with up to fourty carbon atoms;    -   b) an aqueous phase; and    -   c) an oil phase.

The present invention advantageously provides a method for demulsifyingemulsions by using at least one polyorganosiloxane having a molecularstructure comprising a polysiloxane backbone with one or more pendantalkylene oxide groups, one or more pendant groups having the formula(C_(r)H_(2r))B wherein r equals 0 to 30 and B is an aryl radical andoptionally one or more alkyl groups with up to forty carbon atoms. Thedemulsification method disclosed herein is capable of improving theseparation of components in stabilized emulsions while beingcost-effective and practical in a variety of industrial operations.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention is directed to a method for separating thecomponents of an emulsion comprising an oil phase and an aqueous phase.The method comprises incorporating a demulsifying-effective amount of apolyorganosiloxane demulsifier into the emulsion to separate the oilphase from the aqueous phase.

The emulsion can be, for example, a water-in-oil or oil-in-wateremulsion. The emulsions particularly considered herein are those whereinthe emulsified component is in the form of droplets with droplet sizesin the range of about 0.1 microns up to about 200 microns, moretypically about 1-100 microns. The emulsified component can beunstabilized, but is more typically stabilized by a stabilizing amountof a surfactant and/or dispersed particulate solid.

The aqueous phase can be either an emulsified water phase in acontinuous oil phase (i.e., in a water-in-oil emulsion) or a continuouswater phase containing an emulsified oil phase. In either case, theaqueous phase can be essentially pure water, or alternatively, waterwith varying amounts of solid (particulate) materials, salt or otherchemicals.

The oil phase can be either an emulsified oil phase in a continuousaqueous phase (i.e., an oil-in-water emulsion) or a continuous oil phasecontaining an emulsified water phase. In either case, the oil phase isany hydrophobic phase substantially insoluble with the aqueous phase.For example, the oil phase can be composed of one or more hydrophobicchemicals, typically liquids, which individually or in combination aremainly insoluble with the aqueous phase. Such hydrophobic chemicals canbe, for example, linear or branched, cyclic or acyclic, saturated orunsaturated, aliphatic or aromatic hydrocarbons. The hydrocarbonstypically contain at least six carbon atoms and can be unsubstituted, oralternatively, substituted with one or more heteroatoms (e.g., hydroxyl,amino, carboxyl, amide, anhydride, ester, or ether groups) as long asthe hydrocarbons remain mainly insoluble with the aqueous phase.

Some examples of oil phases include halogenated or non-halogenatedC₂-C₃₀ hydrocarbons, and more particularly, halogenated ornon-halogenated ethenes, butadienes, pentanes, hexanes, heptanes,octanes, benzenes, toluene, ethylbenzenes, xylenes, naphthalene,cresols, naphtha, fats, lubrication oils, petroleum, gasoline, crudeoil, fuel oils, jet fuels, heating oils, cleaning oils, vegetable oils,mineral oils, and tar or bitumen derivatives.

It will be understood herein that the terms polyorganosiloxane andorganopolysiloxane are interchangeable with one another. It will also beunderstood that the polyorganosiloxane structures of the presentinvention will assume random distributions of the various buildingblocks therein (i.e., M, D, T and Q units), and a distribution of groups(e.g., alkyleneoxide, alkyl and aryl) among the M, D, T and Q units toprovide average compositions as known within the art.

Other than in the working examples or where otherwise indicated, allnumbers expressing amounts of materials, reaction conditions, timedurations, quantified properties of materials, and so forth, stated inthe specification and claims are to be understood as being modified inall instances by the term “about.”

It will also be understood that any numerical range recited herein isintended to include all sub-ranges within that range and any combinationof the various endpoints of such ranges or subranges.

It will be further understood that any compound, material or substancewhich is expressly or implicitly disclosed in the specification and/orrecited in a claim as belonging to a group of structurally,compositionally and/or functionally related compounds, materials orsubstances includes individual representatives of the group and allcombinations thereof.

The polyorganosiloxane demulsifier has a molecular structure comprisinga polysiloxane backbone of at least two siloxane units covalently boundto (i) one or more alkylene oxide groups, and (ii) one or more arylfunctional groups and (iii) optionally one or more alkyl groups with upto forty carbon atoms.

The polysiloxane backbone of the polyorganosiloxane demulsifier can be alinear, branched, or crosslinked polymeric framework of —Si—O— (siloxy)bonds, and can include any two or more of a combination of M, D, T, andQ groups, wherein, as known in the art, an M group represents amonofunctional group of formula R₃SiO_(1/2), a D group represents abifunctional group of formula R₂SiO_(2/2), a T group represents atrifunctional group of formula RSiO_(3/2), and a Q group represents atetrafunctional group of formula SiO_(4/2). Some examples of classes ofpolysiloxane backbone structures include the MM, MDM, TD, MT, MDT, MDTQ,MQ, MDQ, and MTQ classes of polysiloxanes, and combinations thereof.

The number of siloxane units in the polysiloxane backbone can be two(e.g., MM), but is typically at least three or greater. In oneembodiment, the number of siloxane units is at least three and less thanor equal to about 500. In another embodiment, the number of siloxaneunits is less than 200. For example, for an MD_(n)M type of polysiloxanebackbone, n can be 0, 1, or a number up to about 500, or alternatively,a number not greater than 198.

Typically, the R groups in the polysiloxane backbone are independentlyselected from hydrogen (H), halogen, and linear or branched, cyclic oracyclic, saturated or unsaturated hydrocarbon groups containing one totwenty carbon atoms and optionally heteroatom-substituted with one ormore oxygen and/or nitrogen atoms. Some examples of suitable hydrocarbongroups for R include methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl,n-octyl, isooctyl, n-hexenyl, vinyl, allyl, butenyl, butadienyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl,alkylated phenyl groups, hydroxyl, methoxy, ethoxy, isopropoxy,n-butyloxy, t-butyloxy, isobutyloxy, n-pentoxy, neopentoxy, n-hexoxy,n-heptoxy, n-octoxy, phenoxy, vinyloxy, allyloxy, 2-methoxyethoxy,2-ethoxyethoxy, 2-aminoethoxy, methylamino, dimethylamino, benzylamino,ethanolamino, and diethanolamino groups.

The R groups are more typically hydrocarbon groups, hydroxyl or alkoxygroups containing one to thirty carbon atoms, and even more typicallymethyl, ethyl, methoxy, hydroxyl or ethoxy groups. One or more R groupsof the polysiloxane backbone are necessarily replaced or substituted byone or more alkylene oxide groups and one or more alkyl and/or arylgroups, in accordance with the molecular structure of thepolyorganosiloxane demulsifier described above.

The one or more alkylene oxide groups covalently bound to thepolysiloxane backbone comprise one or more alkylene oxide units. Moretypically, each alkylene oxide group comprises at least 1 and up toabout 100 alkylene oxide units. Each alkylene oxide unit independentlycontains one to six carbon atoms. Some examples of alkylene oxide unitsinclude methyleneoxy (—OCH₂—), ethyleneoxy (—OCH₂CH₂—), propyleneoxy(—OCH(CH₃)CH₂—), trimethyleneoxy (—OCH₂CH₂CH₂—), butyleneoxy (e.g.,—OCH₂CH₂CH₂CH₂—, —OCH(CH₃)CH₂CH₂— or —OCH(CH₃)CH(CH₃)—), andpentamethyleneoxy (—OCH₂CH₂CH₂CH₂CH₂—) units.

In one embodiment, the alkylene oxide group contains only one type ofalkylene oxide unit. For example, the alkylene oxide group can be apolymethylene oxide, polyethylene oxide, polypropylene oxide, orpolybutylene oxide.

In another embodiment, the alkylene oxide group contains at least twodifferent types of alkylene oxide units. For example, the alkylene oxidegroup can be a copolymer having two, three, or four different types ofalkylene oxide units selected from methylene oxide (MO), ethylene oxide(EO), propylene oxide (PO), and butylene oxide (BO) units. Thecopolymers can be block, random, or graft copolymers. Some examples ofblock copolymers include EO-MO, EO-PO, EO-BO, MO-BO, EO-MO-EO, EO-PO-EO,PO-EO-PO and EO-PO-BO types of polymers wherein each MO, EO, PO, and BOin the foregoing examples represents a block of one or more of theindicated alkylene oxide units. According another embodiment of theinvention, more than one kind of polyether can be provided for in themolecule (i.e. hydrosilylation with polyether blends), e.g., all EOpolyether and an all PO polyether in the same component.

In one embodiment, the alkylene oxide group is bound to the polysiloxanebackbone directly, i.e., through a silicon-oxygen bond. In anotherembodiment, the alkylene oxide group is bound to the polysiloxanebackbone indirectly through a linker X, which links a silicon atom ofthe polysiloxane backbone to the alkylene oxide group.

The linking group X is typically an alkylene group (—C_(v)H_(2v)—) wherev is 1 or a higher integer. More typically, X is an alkylene linkinggroup wherein v is 1 to 6, e.g., methylene (—CH₂—), dimethylene(—CH₂CH₂—), or trimethylene (—CH₂CH₂CH₂—). The linker X can also bebranched as in —C(CH₃)₂—, —CH₂CH(CH₃)CH₂—, or —CH₂C(CH₃)₂CH₂—. Thelinker X can also be etherified, as in [(—CH₂—)_(u)—O—(—CH₂—)_(v)]_(w),wherein u and v are independently 0, 1 or a higher integer, and w is 1or a higher integer.

The alkyl and/or aryl functional groups are covalently bound to thepolysiloxane backbone. The alkyl and/or aryl functional groups can becovalently bound directly to one or more silicon atoms of thepolysiloxane backbone, or alternatively, indirectly through a linker,such as X, as described above.

According to an embodiment of the invention a method for separatingemulsions of oil and water, the method comprising incorporating ademulsifying-effective amount of at least one polyorganosiloxane into anemulsion comprising an oil phase and an aqueous phase, thepolyorganosiloxane demulsifier according to the formula:

M¹ _(a)M² _(b)M³ _(c)M⁴ _(d)D¹ _(e)D² _(f)D³ _(g)D⁴ _(h)T¹ _(i)T² _(j)T³_(k)T⁴ _(l)Q_(m)

wherein:

-   -   M¹=R¹R²R³SiO_(1/2)    -   M²=R⁴R⁵R⁶SiO_(1/2)    -   M³=R⁷R⁸R⁹SiO_(1/2)    -   M⁴=R¹⁰R¹¹R¹²SiO_(2/2)    -   D¹=R¹³R¹⁴SiO_(2/2)    -   D²=R¹⁵R¹⁶SiO_(2/2)    -   D³=R¹⁷R¹⁸SiO_(2/2)    -   D⁴=R¹⁹R²⁰SiO_(2/2)    -   T¹=R²¹SiO_(3/2)    -   T²=R²²SiO_(3/2)    -   T³=R²³SiO_(3/2)    -   T⁴=R²⁴SiO_(3/2)    -   Q=SiO_(4/2)        and, R¹ is an alkyl group having from 1 to 12 carbon atoms, an        OH or OR²⁵; R², R³, R⁵, R⁶, R⁸, R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are        alkyl groups having from 1 to 12 carbon atoms; R⁴, R¹⁵, R²² are        (C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶, n        equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals        0 to 50, provided o+p+q≧1; R⁷, R¹⁷, R²³ are branched, linear or        cyclic, saturated or unsaturated alkyl groups having from 4 to        36 carbon atoms; R¹⁰, R¹⁹, R²⁴ are aryl groups having the        general formula (C_(r)H_(2r))B wherein r equals 0-30 and B is an        aryl radical; R¹¹, R¹², R²⁰ are aryl groups having the general        formula (C_(r)H_(2r))B, wherein r equals 0 to 30 or an alkyl        group having from 1 to 12 carbon atoms; R²⁵ is an alkyl group        with 1 to 12 carbon atoms and R²⁶ is a hydrogen or an alkyl        groups having from 1 to 12 carbon atoms, wherein the subscripts        a, b, c, d, e, f, g, h, i, j, k, l, m are zero or positive        integers for molecules subject to the following limitations:        3≦a+b+c+d+e+f+g+h+i+j+k+l+m≦500, b+f+j≧1, c+g+k≧0, d+h+l≧1, and        (a+b+c+d) equals 2+i+j+k+1+2m.

In a specific embodiment of the invention the polyorganosiloxanedemulsifier according to the above-identified formula wherein R¹ is CH₃,OH or OCH₃; R², R³, R⁵, R⁶, R⁸, R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are CH₃; andR¹¹, R¹², R²⁰ are CH_(3.)

In a specific embodiment of the invention: R¹ is CH₃, OH or OCH₃; R²,R³, R⁵, R⁶, R⁸, R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are CH₃, R²⁰ is an arylhaving the formula (C_(r)H_(2r))B and R¹¹, R¹² are either CH₃ or an arylhaving the formula (C_(r)H_(2r))B, with the proviso if thepolyorganosiloxane contains diphenyl R¹⁹ and R²⁰ are C₆H₅.

According to another specific embodiment of the invention, thedemulsifier is a linear polyorganosiloxane according to the formula:

M¹ _(a)M² _(b)M³ _(c)M⁴ _(d)D¹ _(e)D² _(f)D³ _(g)D⁴ _(h)

wherein:

-   -   M¹=R¹R²R³SiO_(1/2)    -   M²=R⁴R⁵R⁶SiO_(1/2)    -   M³=R⁷R⁸R⁹SiO_(1/2)    -   M⁴=R¹⁰R¹¹R¹²SiO_(1/2)    -   D¹=R¹³R¹⁴SiO_(2/2)    -   D²=R¹⁵R¹⁶SiO_(2/2)    -   D³=R¹⁷R¹⁸SiO_(2/2)    -   D⁴=R¹⁹R²⁰SiO_(2/2)        and, R¹ is an alkyl group having from 1 to 12 carbon atoms, an        OH or OR²⁵; R², R³, R⁵, R⁶, R⁸, R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸ are alkyl        groups having from 1 to 12 carbon atoms; R⁴, and R¹⁵, are        (C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶; n        equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals        0 to 50, provided o+p+q≧1; R⁷ and R¹⁷ are linear, branched or        cyclic, saturated or unsaturated alkyl groups having from 4 to        36 carbon atoms; R¹⁰ and R¹⁹ are aryl groups having the general        formula (C_(r)H_(2r))B wherein r equals 0-30 and B is an aryl        radical; R¹¹, R¹², R²⁰ are aryl groups having the general        formula (C_(r)H_(2r))B, wherein r equals 0 to 30 or an alkyl        group having from 1 to 12 carbon atoms; R²⁵ is an alkyl group        with 1 to 12 carbon atoms and R²⁶ is a hydrogen or an alkyl        groups having from 1 to 12 carbon atoms, 3≦a+b+c+d+e+f+g+h≦500,        b+f≧1, c+g≧0, d+h≧1, and a plus b plus c plus d equals 2.

According to one specific embodiment of the invention, the demulsifieris a polyorganosiloxane according to the structure:

wherein X equals 1 to 498, L equals 1 to 300, K equals 0 to 300, Jequals 1 to 300, M equals 0 to 100 N equals 0 to 100, and 0 equals 2 to33 and Z is a hydrogen or an alkyl group having from 1 to 12 carbonatoms.

According to yet another embodiment of the invention the demulsifier isa branched polyorganosiloxane according to the formula:

M¹ _(a)D¹ _(c)D² _(f)D³ _(g)D⁴ _(h)T¹ _(i)T² _(j)T³ _(k)T⁴ _(l)Q_(m)

wherein

-   -   M¹=R¹R²R³SiO_(1/2)    -   D¹=R¹³R¹⁴SiO_(2/2)    -   D²=R¹⁵R¹⁶SiO_(2/2)    -   D³=R¹²R¹⁸SiO_(2/2)    -   D⁴=R¹⁹R²⁰SiO_(2/2)    -   T¹=R²¹SiO_(3/2)    -   T²=R²²SiO_(3/2)    -   T³=R²³SiO_(3/2)    -   T⁴=R²⁴SiO_(3/2)    -   Q=SiO_(4/2)        and, R¹ is an alkyl group having from 1 to 12 carbon atoms, an        OH or OR²⁵; R², R³, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are alkyl groups        having from 1 to 12 carbon atoms; R¹⁵, R²² are        (C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶, n        equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals        0 to 50, provided o+p+q≧1; R¹⁷ and R²³ are linear, branched or        cyclic, saturated or unsaturated alkyl groups having from 4 to        36 carbon atoms; R¹⁹ and R²⁴ are aryl groups having the general        formula (C_(r)H_(2r))B wherein r equals 0-30 and B is an aryl        radical; R²⁰ is an aryl group having the general formula        (C_(r)H_(2r))B, wherein r equals 0 to 30 or an alkyl group        having from 1 to 12 carbon atoms; R²⁵ is an alkyl group with 1        to 12 carbon atoms and R²⁶ is a hydrogen or an alkyl groups        having from 1 to 12 carbon atoms, i+j+k+l+m>0; a=2+i+j+k+l+2m,        3≦a+e+f+g+h+i+j+k+l+m≦500, f+j≧1, g+k≧0, h+l≧1.

According to yet another specific embodiment of the invention, thedemulsifier is a linear polyorganosiloxane according to the formula:

M¹D¹ _(e)D² _(f)D³ _(g)D⁴ _(h)M¹

wherein

-   -   M¹=R¹R²R³SiO_(1/2)    -   D¹=R¹³R¹⁴SiO_(2/2)    -   D²=R¹⁵R¹⁶SiO_(2/2)    -   D³=R¹⁷R¹⁸SiO_(2/2)    -   D⁴=R¹⁹R²⁰SiO_(2/2)        and, R¹ is an alkyl group having from 1 to 12 carbon atoms, an        OH or OR²⁵; R², R³, R³, R¹³, R¹⁴, R¹⁶, R¹⁸ are alkyl groups        having from 1 to 12 carbon atoms; R¹⁵ is        (C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶, n        equals 0 to 6, o equals 0 to 6, o equals 0 to 100 and q equals 0        to 50, provided o+p+q≧1; R¹⁷ is a linear, branched or cyclic,        saturated or unsaturated alkyl groups having from 4 to 36 carbon        atoms; and R¹⁹ is an aryl group having the general formula        (C_(r)H_(2r))B wherein r equals 0-30 and B is an aryl radical;        R²⁰ is an aryl group having the general formula (C_(r)H_(2r))B,        wherein r equal 0 to 30 or an alkyl group having from 1 to 12        carbon atoms; R²⁵ is an alkyl group with 1 to 12 carbon atoms        and R²⁶ is a hydrogen or an alkyl groups having from 1 to 12        carbon atoms, 1≦e+f+g+h≦498, f≧1, g≧0 and h≧1.

In a specific embodiment of the invention the polyorganosiloxanedemulsifier according to the above-identified formula wherein R¹ is CH₃,OH or OCH₃; R², R³, R¹³, R¹⁴, R¹⁶, R¹⁸ are CH₃; and R²⁰ is CH₃.

In a specific embodiment of the invention: R¹ is CH₃, OH or OCH₃; R²,R³, R¹³, R¹⁴, R¹⁶, R¹⁸ is an aryl having the formula (C_(r)H_(2r))B,with the proviso if the polyorganosiloxane contains diphenyl R¹⁹ and R²⁰are C₆H₅.

The polyorganosiloxane demulsifier described above is incorporated intothe emulsion in a demulsifying-effective amount. Ademulsifying-effective amount is an amount that causes the at leastpartial demulsification, i.e., at least partial separation, of the oiland water phases of the emulsion when used alone or with otherdemulsifying agent. In particular embodiments, thedemulsifying-effective amount is, for example, a concentration in therange of about 0.1-10,000 ppm, or about 0.5-1,000 ppm, or about 5-500ppm.

The polyorganosiloxane demulsifier described above can optionally beaccompanied by one or more of any of the well-known organic demulsifierscommonly used in the art. Some classes of such commonly used organicdemulsifiers include hydrocarbon group-containing sulfonic acids (e.g.,dodecylbenzene sulfonic acid), carboxylic acids (e.g., fatty acids),thiocarboxylic acids (e.g., sodium dioctylsulfosuccinate, DOSS),carboxylic acid esters (e.g., fatty acid esters, adipate esters,fumarate esters, and their triol counterparts) phosphinic acids,sulfates (e.g., lauryl sulfate), and phosphates; alkyleneoxide polymersor copolymers and their esters (e.g., the ethylene oxide-propylene oxidecopolymers and/or their combination with formaldehyde resins or di- orpoly-amines); alkyleneoxide-functionalized phenolic resins (e.g.,methylene linked butyl-, octyl-, or nonyl-phenols having EO-P0 copolymerfunctionalization of phenolic groups, see, for example, U.S. Pat. Nos.2,499,368, 2,499,370, 2,524,889, and 2,560,333); epoxy resins (e.g.,those derived from reaction of diglycidyl bis-phenol A with an alkyleneglycol); diepoxides; amine allcyleneoxides (i.e., alkyleneoxide-derivatized amines, e.g., oxyalkylated fatty amide and fatty aminederivatives disclosed in U.S. Pat. No. 5,421,993 or U.S. Publication No.2005/0080221 (Ser. No. 684,250)); polyimine alkoxylates (see, forexample, U.S. Pat. Nos. 3,907,701 and 4,387,028); polyester amines(e.g., EO, PO, and EO/PO copolymers condensed with oxylalkylated fattyamine and a dicarboxylic acid); cationic surfactants (e.g., based onquaternary amines or quaternary ethoxylated amines; see, for example,U.S. Pat. Nos. 3,974,220 and 4,451,671); bis-amides (see, for example,those disclosed in U.S. Pat. No. 4,536,339); and silicone-based polymersor copolymers lacking a combination of one or more alkylene oxide groupsand one or more oxirane-containing and/or oxetane-containing groups(e.g., silicone polyethers as disclosed in U.S. Pat. No. 4,596,653 andalkylsilicone polyether terpolymers as disclosed in U.S. Pat. No.5,004,559); and salts thereof.

When the organic demulsifier is included, the weight ratio of thepolyorganosiloxane demulsifier (either the structures of this inventionalone or in combination with other silicones, which are not part of thisinvention) to the organic demulsifier is typically in the range of about100:1 to about 1:1000, more typically in the range of about 5:1 to about1:200.

The incorporation of the demulsifier can be achieved by any method knownin the art for integrally mixing the demulsifier with the emulsion. Themixing procedure can use, for example, standard mixers, high-speedmixers or blenders, or shakers. The temperature can be unadjusted withinroom temperature limits (˜20-30° C.), or adjusted as required, forexample, to 40-150° C. for a suitable amount of time.

According to another embodiment, when the polyorganosiloxane demulsifierof the invention is either used alone or accompanied by additionalsilicone and/or organic demulsifiers it can be as a blend, solution, adispersion, or either an oil-in-water or a water-in-oil emulsion ormicroemulsion.

In another aspect, the invention is directed to a composition comprisingthe demulsifying-effective amount of polyorganosiloxane demulsifier,described above, and the components of the emulsion into which thepolyorganosiloxane demulsifier was incorporated. For example, thecomposition can include the polyorganosiloxane demulsifier, an aqueousphase, and an oil phase.

According to another embodiment, a solid filler (e.g., drilling mud andthe like can be included in the composition or method described abovefor breaking emulsions. By “solid filler” is meant solid materials inthe form of particles, which is intentionally added to an emulsion or atleast one of the liquid phases of the emulsion in order to fill a gap ormodify the properties of the emulsion. Also contemplated within thescope of the invention are such residual or trace amounts of solidswhich correspond to the amounts typically encountered after substantialremoval of solids by, for example, filtration. Such residual or traceamounts can remain and provide no function to the composition.

One method of producing component (a) i.e., the polyorganosiloxanedemulsifier of the present invention is to react a molecule of thefollowing formula:

M^(H) _(x)M¹ _(u) D^(H) _(y)D¹ _(v)D⁴ _(h)T^(H) _(z)T¹ _(w)Q_(m)

wherein:

M^(H) _(x,) D^(H) _(y,) T^(H) _(z), are the hydride precursors to the M,D and T structural units in the composition of the present invention,and D⁴ _(h) is diphenyl-silicone, (C₆H₅)₂SiO_(2/2), wherein thedefinitions and relationships are consistent with those defined above,under hydrosilylation conditions, with:

1. an olefinically modified polyalkyleneoxide;

such as allyloxypolyethyleneglycol, or methallyloxypolyalkyleneoxide,which are incorporated herein as examples, and not set forth to limitother possible olefinically modified alkyleneoxide components. As usedherein the phrase “olefinically modified polyalkyleneoxide” is definedas a molecule possessing one or more alkyleneoxide groups containing oneor more, terminal or pendant, carbon-carbon double bonds. The polyetheris an olefinically modified polyalkyleneoxide (hereinafter referred toas “polyether”) is described by the general formula :

CH₂═CH(R²⁷)(R²⁸)_(s)O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶

wherein; R²⁷ is H or methyl; R²⁸ is a divalent alkyl radical of 1 to 6carbons where the subscript s may be 0 or 1. When the polyether iscomposed of mixed oxyalkyleneoxide groups (i.e. oxyethylene,oxypropylene and oxybutylene) the units may be blocked, or randomlydistributed. One skilled in the art will understand the advantages ofusing a blocked or random configuration. Illustrative examples ofblocked configurations are: -(oxyethylene)_(a)(oxypropylene)_(b)-;-(oxybutylene),(oxyethylene),-; and-(oxypropylene)_(b)(oxyethylene)_(a)(oxybutylene)_(c)-.

Illustrative examples of the polyether are provided below, but notlimited to:

-   CH₂═CHCH₂O(CH₂CH₂O)₈H; CH₂═CHCH₂O(CH₂CH₂O)₈CH₃;-   CH₂═CHCH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅H;-   CH₂═CHO(CH₂CH₂O)₅(CH₂CH(CH₃)O)₅H;-   CH₂═C(CH₃)CH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅C(═O)CH_(3;)-   CH₂═CHCH₂O(CH₂CH₂O)₅(CH₂CH(CH₃)O)₂(CH₂CH(CH₂CH₃)O)₂H;

2. an olefinically modified aromatic:

As used herein the phrase “olefinically modified aromatic” is defined asa molecule possessing one or more aryl groups containing one or more,terminal or pendant, carbon-carbon double bonds, as described by thegeneral formula :

CH₂═CH—B₁

wherein; B₁ is a monovalent aryl radical; and,

3. optionally, olefinically modified alkyl: As used herein the phrase“olefinically modified alkyl” is defined as a molecule possessing one ormore alkyl groups containing one or more, terminal or pendant,carbon-carbon double bonds, as described by the general formula :

CH₂═CH—R²⁹

wherein; R²⁹ is a monovalent alkyl radical having from 1 to 10 carbonatoms or H.

Precious metal catalysts suitable for making organic-substitutedsiloxanes are also well known in the art and comprise complexes ofrhodium, ruthenium, palladium, osmium, iridium, and/or platinum. Manytypes of platinum catalysts for this SiH olefin addition reaction areknown and such platinum catalysts may be used to generate thecompositions of the present invention. The platinum compound can beselected from those having the formula (PtCl₂Olefin) and H(PtCl₃Olefin)as described in U.S. Pat. No. 3,159,601, hereby incorporated byreference. A further platinum containing material can be a complex ofchloroplatinic acid with up to 2 moles per gram of platinum of a memberselected from the class consisting of alcohols, ethers, aldehydes andmixtures thereof as described in U.S. Pat. No. 3,220,972 herebyincorporated by reference. Yet another group of platinum containingmaterials useful in this present invention is described in U.S. Pat.Nos. 3,715,334; 3,775,452 and 3,814,730 (Karstedt). Additionalbackground concerning the art may be found in J. L. Spier, “HomogeneousCatalysis of Hydrosilation by Transition Metals”, in Advances inOrganometallic Chemistry, volume 17, pages 407 through 447, F. G. A.Stone and R. West editors, published by Academic Press (New York, 1979).Those skilled in the art can easily determine an effective amount ofplatinum catalyst. Generally an effective amount ranges from about 0.1to 50 parts per million of the total organomodified siloxanecomposition.

The following examples show that the demulsifying properties of thepolyorganosiloxane copolymers, which are to be used pursuant to theinvention, are superior to those known from the art, the examples beinggiven by way of illustration and not by way of limitation.

EXAMPLE 1

Preparation of (CH₃)₃Si(OSi(CH₃)₂)₇₅(OSi(H)(CH₃))₃₆ OSi(CH₃)₃Polymethylhydrogen-co-dimethylsiloxane fluid with average formula(CH₃)₃Si(OSi(CH₃)₂)₇₅OSi(H)(CH₃))₃₆OSi(CH₃)₃ was prepared by acidcatalyzed ring opening polymerization of polymethylhydrogensiloxane withthe average formula (CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃ andoctamethylcyclotetrasiloxane (D₄, from Momentive Performance Materials,Wilton, Conn.) in the presence of Tulison TP63, an acidic ion exchangeresin (IER, from Thermax Ltd, India). The reaction was carried out bymixing 216 g of (CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃, 555 g D₄ and 7.5 g ofIER at 60° C. for 24 hrs in a round bottom flask fitted with acondenser. At the end of the reaction the IER was filtered out and thefinal non-volatile fraction in the resulting copolymer was found to be92%. The average structure was determined by ²⁹Si—NMR.

EXAMPLE 2

Preparation of (CH₃)₃Si(OSi(CH₃)₂)₇₅(OSi(H)(CH₃))_(13.3)OSi(CH₃)₃Polymethylhydrogen-co-dimethylsiloxane fluid with average formula(CH₃)₃Si(OSi(CH₃)₂)₇₅(OSi(H)(CH₃))_(13.3)OSi(CH₃)₃ was prepared by acidcatalyzed ring opening polymerization of hexamethyldisiloxane (MM, fromSigma Aldrich, USA) polymethylhydrogensiloxane with the average formula(CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃ (from Momentive Performance Materials,Wilton, Conn.) and D_(4,) in the presence of Tulison TP63 IER. Thereaction was carried out by mixing 10.2 g of MM, 216 g of(CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃, 555 g D₄ and 7.5 g of IER, at 50° C.for 24 hrs in a round bottom flask fitted with a condenser. At the endof the reaction the IER was filtered out and the final non-volatilefraction in the resulting copolymer was found to be 90%. The averagestructure was determined by ²⁹Si-NMR

EXAMPLE 3

Preparation of (CH₃)₃Si(OSi(CH₃)₂)₂(OSi(C₆H₅)₂)₂(OSi(H)(CH₃))_(13.3)OSi(CH₃)₃Polymethylhydrogen-co-dimethyl-codiphenylsiloxane terpolymer withaverage formula(CH₃)₃Si(OSi(CH₃)₂)₂(OSi(C₆H₅)₂)₂(OSi(H)(CH₃))_(13.3)OSi(CH₃)₃ wasprepared by acid catalyzed ring opening polymerizationPolydimethyl-co-diphenylsiloxane with the average formula(CH₃)₃Si(OSi(CH₃)₂)₂(OSi(C₆H₅)₂)₂OSi(CH₃)₃ (from Performance Materials,Wilton, Conn.) and tetramethylcyclo-tetrasiloxane (D^(H) ₄, from Gelest,Tullytown, Pa.), in the presence of Tulison TP63 IER. The reaction wascarried out by mixing 46.6 g of polydimethyl-co-diphenylsiloxane, 80 gD^(H) ₄ and 1.5 g of IER at 80° C. for 24 hrs in a round bottom flaskfitted with a condenser. At the end of the reaction the IER was filteredout and the final non-volatile fraction in the resulting copolymer wasfound to be 90%. The average structure was determined by ²⁹Si-NMR

EXAMPLE 4

Preparation of (CH₃)₃Si(OSi(CH₃)₂)₂(OSi(H)(CH₃))₁₄OSi(CH₃)₃Polymethylhydrogen-co-dimethylsiloxane fluid with the average formula(CH₃)₃Si(OSi(CH₃)₂)₂(OSi(H)(CH₃))₁₄OSi(CH₃)₃ was prepared by acidcatalyzed ring opening polymerization of MM, polymethylhydrogensiloxanewith the average formula (CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃ (fromMomentive Performance Materials, Wilton, Conn.) and D₄, in the presenceof Tulison TP63 IER. The reaction was carried out by mixing 10 g of MM,216 g of (CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃, 15 g D₄ and 2.5 g of IER at50° C. for 24 hrs in a round bottom flask fitted with a condenser. Atthe end of the reaction the IER was filtered out and the finalnon-volatile fraction in the resulting copolymer was found to be 89%.The average structure was determined by ²⁹Si-NMR

EXAMPLE 5

Preparation of (CH₃)₃Si(OSi(H)(CH₃))₁₄ OSi(CH₃)₃Polymethylhydrogen-co-dimethylsiloxane fluid with the average formula(CH₃)₃Si(OSi(CH₃)₂)₂(OSi(H)(CH₃))₁₄OSi(CH₃)₃ was prepared by acidcatalyzed equilibration of MM and polymethylhydrogen-siloxane with theaverage formula (CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃ (from MomentivePerformance Materials, Wilton, Conn.), in the presence of Tulison TP63IER. The reaction was carried out by mixing 10 g of MM, 216 g of(CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃ and 2.5 g of IER at 50° C. for 24 hrsin a round bottom flask fitted with a condenser. At the end of thereaction the IER was filtered out and the final non-volatile fraction inthe resulting copolymer was found to be 87%. The average structure wasdetermined by ²⁹Si-NMR.

EXAMPLE 6

Preparation of (CH₃)₃Si(OSi(CH₃)₂)₈₅(OSi(H)(CH₃))₃₆OSi(CH₃)₃Polymethylhydrogen-co-dimethylsiloxane fluid with the average formula(CH₃)₃Si(OSi(CH₃)₂)₇₅(OSi(H)(CH₃))₃₆OSi(CH₃)₃ was prepared by acidcatalyzed ring opening polymerization of polymethylhydrogensiloxane withthe average formula (CH₃)₃SI(OSi(H)(CH₃))₃₆OSi(CH₃)₃ (from MomentivePerformance Materials, Wilton, Conn.) and D₄, in the presence of TulisonTP63 IER. The reaction was carried out by mixing 216 g of(CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃, 630 g of D₄ and 7.5 g of IER at 60° C.for 24 hrs in a round bottom flask fitted with a condenser. At the endof the reaction the IER was filtered out and the final non-volatilefraction in the resulting copolymer was found to be 90%. The averagestructure was determined by ²⁹Si-NMR.

EXAMPLE 7

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)₂(Si(R₃)(CH₃)O)₂₀(Si(R⁴)(CH₃)O)₁₄Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between Example 1, 1-octene, alphamethylstyrene (AMS) and apolyether with the average formula of CH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 1. The reactorwas heated to 74° C. and Karstedt's catalyst equivalent to 5 ppm ofPlatinum was dissolved in 8.4 g of AMS was added to the reaction vessel.The reaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS wasconsumed (as confirmed by H-NMR). Then 4.9 g of allyl polyether abovewas charged into the reactor followed by immediate addition of 11.4 g of1-octene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and the temperatureincreased to about 110° C. The reaction mixture turned from aheterogeneous system to a homogeneous one and the heating was continuedat 100° C. for another three hours until all the hydrides were consumed(as confirmed by H-NMR). The copolymer was allowed to cool with stirringin the reactor for 30 minutes and then removed.

EXAMPLE 8

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(3.5)(Si(R³)(CH₃)O)_(23.5)(Si(R⁴)(CH₃)O)₁₀Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between Example 1, 1-octene, alphamethylstyrene (AMS) and apolyether with the average formula of CH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 1. The reactorwas heated to 74° C. and Karstedt's catalyst equivalent to 5 ppm ofPlatinum was dissolved in 6.0 g of AMS was added to the reaction vessel.The reaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS wasconsumed (as confirmed by H-NMR). Then 8.5 g of allyl polyether abovewas charged into the reactor followed by immediate addition of 13.3 g of1-octene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and the temperatureincreased to about 110° C. The reaction mixture turned from aheterogeneous system to a homogeneous one and the heating was continuedat 100° C. for another three hours until all the hydrides were consumed(as confirmed by H-NMR). The copolymer was allowed to cool with stirringin the reactor for 30 minutes and then removed.

EXAMPLE 9

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(5.75)(Si(R³)(CH₃)O)_(23.8)(Si(R⁴)(CH₃)O)_(6.5)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 3.9 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then14.1 g of allyl polyether above was charged into the reactor followed byimmediate addition of 13.3 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 10

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)₇(Si(R³)(CH₃)O)_(25.4)(Si(R⁴)(CH₃)O)_(3.6)Si(CH₃)In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 2.2 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then17.1 g of allyl polyether above was charged into the reactor followed byimmediate addition of 14.5 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 11

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(10.8)(Si(R³)(CH₃)O)_(21.6)(Si(R⁴)(CH₃)O)_(3.6)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 2.2 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then26.4 g of allyl polyether above was charged into the reactor followed byimmediate addition of 12.3 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 12

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(10.8)(Si(R³)(CH₃)O)_(10.8)(Si(R⁴)(CH₃)O)_(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 8.6 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then26.4 g of allyl polyether above was charged into the reactor followed byimmediate addition of 6.1 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 13

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(10.8)(Si(R³)(CH₃)O)₅(Si(R⁴)(CH₃)O)₂₁Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 12.5 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then26.4 g of allyl polyether above was charged into the reactor followed byimmediate addition of 2.8 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 14

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(10.8)(Si(R³)(CH₃)O)_(16.2)(Si(R⁴)(CH₃)O)₉Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 5.4 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then26.4 g of allyl polyether above was charged into the reactor followed byimmediate addition of 9.2 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 15

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(16.2)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)O)_(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 8.6 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then39.6 g of allyl polyether above was charged into the reactor followed byimmediate addition of 3.1 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 16

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(21.6)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)O)₉Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 5.4 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then52.8 g of allyl polyether above was charged into the reactor followed byimmediate addition of 3.1 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 17

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(21.6)(Si(R³)(CH₃)O)_(10.8)(Si(R⁴)(CH₃)O)_(3.6)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 2.2 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then52.8 g of allyl polyether above was charged into the reactor followed byimmediate addition of 6.1 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

EXAMPLE 18

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(21.6)(Si(R⁴)(CH₃)O)^(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH and R⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, AMS and apolyether with the average formula of CH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 1. The reactorwas heated to 74° C. and Karstedt's catalyst equivalent to 5 ppm ofPlatinum was dissolved in 8.6 g of AMS was added to the reaction vessel.The reaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS isconsumed (as confirmed by H-NMR). Then 52.8 g of allyl polyether abovewere charged into the reactor followed by immediate addition of 50 mL oftoluene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and temperatureincreased to about 100° C. Reaction mixture turns from a heterogeneoussystem to a homogeneous one and was continued at 100° C. for anotherfive hours when all the hydrides were consumed (as confirmed by H-NMR).Solvent was removed under reduced pressure and the copolymer was allowedto cool with stirring in the reactor for 30 minutes and then removed.

EXAMPLE 19

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(21.6)(Si(R⁴)(CH₃)O)_(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂OH and R⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, AMS and apolyether with the average formula of CH₂═CHCH₂(OCH₂CH₂)₁₂OH. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 1. The reactorwas heated to 74° C. and Karstedt's catalyst equivalent to 5 ppm ofPlatinum was dissolved in 8.6 g of AMS was added to the reaction vessel.The reaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS isconsumed (as confirmed by H-NMR). Then 81.3 g of allyl polyether abovewere charged into the reactor followed by immediate addition of 50 mL oftoluene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and temperatureincreased to about 100° C. Reaction mixture turns from a heterogeneoussystem to a homogeneous one and was continued at 100° C. for anotherfive hours when all the hydrides were consumed (as confirmed by H-NMR).Solvent was removed under reduced pressure and the copolymer was allowedto cool with stirring in the reactor for 30 minutes and then removed.

EXAMPLE 20

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(21.6)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)O)_(9.9)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₄OH, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₄OH. A nitrogen blanketed glass reactorat atmospheric pressure, which was equipped with a temperature probe, anagitator, a condenser and a nitrogen inlet, was charged with 40 g ofpolysiloxane hydride from Example 1. The reactor was heated to 74° C.and Karstedt's catalyst equivalent to 5 ppm of Platinum was dissolved in5.9 g of AMS was added to the reaction vessel. The reaction wasexothermic and the reactor temperature rose to 100° C. within 2 minutes.The reaction was continued till all the AMS was consumed (as confirmedby H-NMR). Then 106.3 g of allyl polyether above was charged into thereactor followed by immediate addition of 3.1 g of 1-octene containingKarstedt's catalyst equivalent to 5 ppm of Platinum to the reactor. Thisreaction was also exothermic and the temperature increased to about 110°C. The reaction mixture turned from a heterogeneous system to ahomogeneous one and the heating was continued at 100° C. for anotherthree hours until all the hydrides were consumed (as confirmed byH-NMR). The copolymer was allowed to cool with stirring in the reactorfor 30 minutes and then removed.

EXAMPLE 21

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(21.6)(Si(R³)(CH₃)O)_(3.4)(Si(R⁴)(CH₃)O)_(9.9)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₁₅OH, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂M(OCH₂CH(CH₃))₁₅OH. A nitrogen blanketed glass reactorat atmospheric pressure, which was equipped with a temperature probe, anagitator, a condenser and a nitrogen inlet, was charged with 40 g ofpolysiloxane hydride from Example 1. The reactor was heated to 74° C.and Karstedt's catalyst equivalent to 5 ppm of Platinum was dissolved in5.9 g of AMS was added to the reaction vessel. The reaction wasexothermic and the reactor temperature rose to 100° C. within 2 minutes.The reaction was continued till all the AMS was consumed (as confirmedby H-NMR). Then 225.3 g of allyl polyether above was charged into thereactor followed by immediate addition of 3.1 g of 1-octene containingKarstedt's catalyst equivalent to 5 ppm of Platinum to the reactor. Thisreaction was also exothermic and the temperature increased to about 110°C. The reaction mixture turned from a heterogeneous system to ahomogeneous one and the heating was continued at 100° C. for anotherthree hours until all the hydrides were consumed (as confirmed byH-NMR). The copolymer was allowed to cool with stirring in the reactorfor 30 minutes and then removed.

EXAMPLE 22

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(16.2)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)O)_(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₄OH, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₄OH. A nitrogen blanketed glass reactorat atmospheric pressure, which was equipped with a temperature probe, anagitator, a condenser and a nitrogen inlet, was charged with 40 g ofpolysiloxane hydride from Example 1. The reactor was heated to 74° C.and Karstedt's catalyst equivalent to 5 ppm of Platinum was dissolved in8.6 g of AMS was added to the reaction vessel. The reaction wasexothermic and the reactor temperature rose to 100° C. within 2 minutes.The reaction was continued till all the AMS was consumed (as confirmedby H-NMR). Then 80.3 g of allyl polyether above was charged into thereactor followed by immediate addition of 3.1 g of 1-octene containingKarstedt's catalyst equivalent to 5 ppm of Platinum to the reactor. Thisreaction was also exothermic and the temperature increased to about 110°C. The reaction mixture turned from a heterogeneous system to ahomogeneous one and the heating was continued at 100° C. for anotherthree hours until all the hydrides were consumed (as confirmed byH-NMR). The copolymer was allowed to cool with stirring in the reactorfor 30 minutes and then removed.

EXAMPLE 23

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(16.2)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)(O)_(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₁₅OH, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₁₅)H. A nitrogen blanketed glassreactor at atmospheric pressure, which was equipped with a temperatureprobe, an agitator, a condenser and a nitrogen inlet, was charged with40 g of polysiloxane hydride from Example 1. The reactor was heated to74° C. and Karstedt's catalyst equivalent to 5 ppm of Platinum wasdissolved in 8.6 g of AMS was added to the reaction vessel. The reactionwas exothermic and the reactor temperature rose to 100° C. within 2minutes. The reaction was continued till all the AMS was consumed (asconfirmed by H-NMR). Then 176 g of allyl polyether above was chargedinto the reactor followed by immediate addition of 3.1 g of 1-octenecontaining Karstedt's catalyst equivalent to 5 ppm of Platinum to thereactor. This reaction was also exothermic and the temperature increasedto about 110° C. The reaction mixture turned from a heterogeneous systemto a homogeneous one and the heating was continued at 100° C. foranother three hours until all the hydrides were consumed (as confirmedby H-NMR). The copolymer was allowed to cool with stirring in thereactor for 30 minutes and then removed.

EXAMPLE 24

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(16.2)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)O)_(14.4)Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₃₆(OCH₂CH(CH₃))₄₁OH, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₃₆(OCH₂CH(CH₃))₄₁OH. A nitrogen blanketed glassreactor at atmospheric pressure, which was equipped with a temperatureprobe, an agitator, a condenser and a nitrogen inlet, was charged with40 g of polysiloxane hydride from Example 1. The reactor was heated to74° C. and Karstedt's catalyst equivalent to 5 ppm of Platinum wasdissolved in 8.6 g of AMS was added to the reaction vessel. The reactionwas exothermic and the reactor temperature rose to 100° C. within 2minutes. The reaction was continued till all the AMS was consumed (asconfirmed by H-NMR). Then 379 g of allyl polyether above was chargedinto the reactor followed by immediate addition of 3.1 g of 1-octenecontaining Karstedt's catalyst equivalent to 5 ppm of Platinum to thereactor. This reaction was also exothermic and the temperature increasedto about 110° C. The reaction mixture turned from a heterogeneous systemto a homogeneous one and the heating was continued at 100° C. foranother three hours until all the hydrides were consumed (as confirmedby H-NMR). The copolymer was allowed to cool with stirring in thereactor for 30 minutes and then removed.

EXAMPLE 25

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅Si(R²)(CH₃)O)_(5.2)(Si(R³)(CH₃)O)₆(Si(R⁴)(CH₃)O)₂Si(CH₃)₃In the above formula, R² is a mixture of two polyether copolymers havingthe average formulas —CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH(CH₃)CH₂)₁₅OH and—CH₂CH₂CH₂—(OCH₂CH₂)₃₆(OCH(CH₃)CH₂)₄₁OH such that the combined averagemolecular weight is approximately 2250 g/mol, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 2, 1-octene,alphamethylstyrene (AMS) and blend of polyethers with the averageformula of CH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₁₅OH andCH₂═CHCH₂(OCH₂CH₂)₃₆(OCH₂CH(CH₃))₄₁OH in 3:1 molar ratio. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a)nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 2. The reactorwas heated to 74° C. and Karstedt's catalyst equivalent to 5 ppm ofPlatinum was dissolved in 1.5 g of AMS was added to the reaction vessel.The reaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS wasconsumed (as confirmed by H-NMR). Then 106.8 g of allyl polyether abovewas charged into the reactor followed by immediate addition of 4.1 g of1-octene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and the temperatureincreased to about 110° C. The reaction mixture turned from aheterogeneous system to a homogeneous one and the heating was continuedat 100° C. for another three hours until all the hydrides were consumed(as confirmed by H-NMR). The copolymer was allowed to cool with stirringin the reactor for 30 minutes and then removed.

EXAMPLE 26

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)₈(Si(R³)(CH₃)O)₄(Si(R⁴)(CH₃)O)_(1.2)Si(CH₃)₃In the above formula, R² is a mixture of two polyether copolymers havingthe average formulas —CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH(CH₃)CH₂)₁₅OH and—CH₂CH₂CH₂—(OCH₂CH₂)₃₆(OCH(CH₃)CH₂)41OH such that the combined averagemolecular weight is approximately 2250 g/mol, R³ is a n-octyl group andR⁴ is 2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 2, 1-octene,alphamethylstyrene (AMS) and blend of polyethers with the averageformula of CH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₁₅OH andCH₂═CHCH₂(OCH₂CH)₂)₃₆(OCH₂CH(CH₃))₄₁OH in 3:1 molar ratio. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 2. The reactorwas heated to 74° C. and Karstedt's catalyst equivalent to 5 ppm ofPlatinum was dissolved in 0.9 g of AMS was added to the reaction vessel.The reaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS wasconsumed (as confirmed by H-NMR). Then 164.4 g of allyl polyether abovewas charged into the reactor followed by immediate addition of 2.8 g of1-octene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and the temperatureincreased to about 110° C. The reaction mixture turned from aheterogeneous system to a homogeneous one and the heating was continuedat 100° C. for another three hours until all the hydrides were consumed(as confirmed by H-NMR). The copolymer was allowed to cool with stirringin the reactor for 30 minutes and then removed.

EXAMPLE 27

Preparation of (CH₃)₃SiO(Si(CH₃)₂O)₂(Si(R²)(CH₃)O)₆(Si(R³)(CH₃)O)₆(SiR⁴₂O)₂Si(CH₃)₃ In the above formula, R² is a polyether copolymers havingthe average formula—CH₂CH₂CH₂(OCH₂CH₂)₁₂OH, R³ is a n-octyl group and R⁴is phenyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 3, 1-octene and apolyether with the average formula of CH₂═CHCH₂(OCH₂CH₂)₁₂OH. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 3. The reactorwas heated to 74° C. and 137 g of allyl polyether above was charged intothe reactor followed by immediate addition of 20.7 g of 1-octenecontaining Karstedt's catalyst equivalent to 10 ppm of Platinum to thereactor. This reaction was also exothermic and temperature increased toabout 100° C. Reaction mixture turns from a heterogeneous system to ahomogeneous one and was continued at 100° C. for another four hours whenall the hydrides were consumed (as confirmed by H-NMR).

EXAMPLE 28

Preparation of (CH₃)₃SiO(Si(CH₃)₂O)₂(Si(R²)(CH₃)O)₆(Si(R³)(CH₃)O)₆(SiR⁴₂O)₂Si(CH₃)₃ In the above formula, R² is a polyether copolymers havingthe average formula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴is phenyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 3, 1-octene and apolyether with the average formula of CH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogenblanketed glass reactor at atmospheric pressure, which was equipped witha temperature probe, an agitator, a condenser and a nitrogen inlet, wascharged with 40 g of polysiloxane hydride from Example 3. The reactorwas heated to 74° C. and 88.9 g of allyl polyether above was chargedinto the reactor followed by immediate addition of 20.7 g of 1-octenecontaining Karstedt's catalyst equivalent to 10 ppm of Platinum to thereactor. This reaction was also exothermic and temperature increased toabout 100° C. Reaction mixture turns from a heterogeneous system to ahomogeneous one and was continued at 100 C for another four hours whenall the hydrides were consumed (as confirmed by H-NMR).

EXAMPLE 29

Preparation of (CH₃)₃SiO(Si(CH₃)₂O)₂(Si(R²)(CH₃)O)₆(Si(R³)(CH₃)O)₆(SiR⁴₂O)₂Si(CH₃)₃ In the above formula, R² is a polyether copolymers havingthe average formula—CH₂CH₂CH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₄OH, R³ is an-octyl group and R⁴ radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 3, 1-octene and apolyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₄OH. A nitrogen blanketed glass reactorat atmospheric pressure, which was equipped with a temperature probe, anagitator, a condenser and a nitrogen inlet, was charged with 40 g ofpolysiloxane hydride from Example 3. The reactor was heated to 74° C.and 180 g of allyl polyether above was charged into the reactor followedby immediate addition of 20.7 g of 1-octene containing Karstedt'scatalyst equivalent to 10 ppm of Platinum to the reactor. This reactionwas also exothermic and temperature increased to about 100° C. Reactionmixture turns from a heterogeneous system to a homogeneous one and wascontinued at 100° C. for another four hours when all the hydrides wereconsumed (as confirmed by H-NMR).

EXAMPLE 30

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₂(Si(R²)(CH₃)O)₆(Si(R³)(CH₃)O)₆(Si(R⁴)(CH₃)O)₂Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical

This laboratory prepared material was obtained from the hydrosilylationreaction between polysiloxane hydride from Example 4, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₁₂OH. A nitrogen blanketed glass reactor atatmospheric pressure, which was equipped with a temperature probe, anagitator, a condenser and a nitrogen inlet, was charged with 40 g ofpolysiloxane hydride from Example 4. The reactor was heated to 74° C.and Karstedt's catalyst equivalent to 5 ppm of Platinum was dissolved in8.2 g of AMS was added to the reaction vessel. The reaction wasexothermic and the reactor temperature rose to 100° C. within 2 minutes.The reaction was continued till all the AMS was consumed (as confirmedby H-NMR). Then 158 g of allyl polyether above was charged into thereactor followed by immediate addition of 23.4 g of 1-octene containingKarstedt's catalyst equivalent to 5 ppm of Platinum to the reactor. Thisreaction was also exothermic and the temperature increased to about 110°C. The reaction mixture turned from a heterogeneous system to ahomogeneous one and the heating was continued at 100° C. for anotherthree hours until all the hydrides were consumed (as confirmed byH-NMR). The copolymer was allowed to cool with stirring in the reactorfor 30 minutes and then removed.

EXAMPLE 31

Preparation of(CH₃)₃SiO(Si(R²)(CH₃)O)₆(Si(R³)(CH₃)O)₆(Si(R⁴)(CH₃)O)₄Si(CH₃)₃ In theabove formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₁₂OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 5, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₁₂(OCH₂CH(CH₃))₁₅OH. A nitrogen blanketed glassreactor at atmospheric pressure, which was equipped with a temperatureprobe, an agitator, a condenser and a nitrogen inlet, was charged with40 g of polysiloxane hydride from Example 5. The reactor was heated to74° C. and Karstedt's catalyst equivalent to 5 ppm of Platinum wasdissolved in 16.8 g of AMS was added to the reaction vessel. Thereaction was exothermic and the reactor temperature rose to 100° C.within 2 minutes. The reaction was continued till all the AMS wasconsumed (as confirmed by H-NMR). Then 158 g of ally! polyether abovewas charged into the reactor followed by immediate addition of 23.9 g of1-octene containing Karstedt's catalyst equivalent to 5 ppm of Platinumto the reactor. This reaction was also exothermic and the temperatureincreased to about 110° C. The reaction mixture turned from aheterogeneous system to a homogeneous one and the heating was continuedat 100° C. for another three hours until all the hydrides were consumed(as confirmed by H-NMR). The copolymer was allowed to cool with stirringin the reactor for 30 minutes and then removed.

EXAMPLE 32

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₈₅(Si(R²)(CH₃)O)_(8.5)(Si(R³)(CH₃)O)_(22.5)(Si(R⁴)(CH₃)O)₅Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OCH₃, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 6, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OCH₃. A nitrogen blanketed glass reactor atatmospheric pressure, which was equipped with a temperature probe, anagitator, a condenser and a nitrogen inlet, was charged with 40 g ofpolysiloxane hydride from Example 6. The reactor was heated to 74° C.and Karstedt's catalyst equivalent to 5 ppm of Platinum was dissolved in2.7 g of AMS was added to the reaction vessel. The reaction wasexothermic and the reactor temperature rose to 100° C. within 2 minutes.The reaction was continued till all the AMS was consumed (as confirmedby H-NMR). Then 20 g of allyl polyether above was charged into thereactor followed by immediate addition of 11.7 g of 1-octene containingKarstedt's catalyst equivalent to 5 ppm of Platinum to the reactor. Thisreaction was also exothermic and the temperature increased to about 110°C. The reaction mixture turned from a heterogeneous system to ahomogeneous one and the heating was continued at 100° C. for anotherthree hours until all the hydrides were consumed (as confirmed byH-NMR). The copolymer was allowed to cool with stirring in the reactorfor 30 minutes and then removed.

EXAMPLE 33

Preparation of(CH₃)₃SiO(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(5.2)(Si(R³)(CH₃)O)_(25.8)(Si(R⁴)(CH₃)O)₅Si(CH₃)₃In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 1, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst equivalent to 5 ppm of Platinum was dissolved in 3 g of AMS wasadded to the reaction vessel The reaction was exothermic and the reactortemperature rose to 100° C. within 2 minutes. The reaction was continuedtill all the AMS was consumed (as confirmed by H-NMR). Then 12.7 g ofallyl polyether above was charged into the reactor followed by immediateaddition of 14.7 g of 1-octene containing Karstedt's catalyst equivalentto 5 ppm of Platinum to the reactor. This reaction was also exothermicand the temperature increased to about 110° C. The reaction mixtureturned from a heterogeneous system to a homogeneous one and the heatingwas continued at 100° C. for another three hours until all the hydrideswere consumed (as confirmed by H-NMR). The copolymer was allowed to coolwith stirring in the reactor for 30 minutes and then removed.

EXAMPLE 34

Preparation of ((CH₃)₃SiO_(1/2))_(2.5)(OSi(CH₃)₂)₇₅(OSi(H)(CH₃))₃₆(SiO₂)Branched polymethylhydrogen-co-dimethylsiloxane fluid with the aboveaverage formula was prepared by acid catalyzed ring openingpolymerization of polymethylhydrogensiloxane with the average formula(CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃, MQ resin, with the average formula((CH₃)₃SiO_(1/2))_(1.0)(SiO₂)_(1.0) and a viscosity of 1000-20000 cStand D₄ (all from Momentive Performance Materials, Wilton, Conn.), in thepresence of Tulison TP63 IER. The reaction was carried out by mixing 216g of (CH₃)₃Si(OSi(H)(CH₃))₃₆OSi(CH₃)₃, 555 g D₄, 22.2 g of MQ resin and7.5 g of TP63 IER at 80° C. for 24 hrs in a round bottom flask fittedwith a condenser. At the end of the reaction the TP63 IER was filteredout and the final non-volatile fraction in the resulting copolymer wasfound to be 88%. The average structure was determined by ²⁹Si-NMR.

EXAMPLE 35

Preparation of((CH₃)₃SiO)_(2.5)(Si(CH₃)₂O)₇₅(Si(R²)(CH₃)O)_(16.2)(Si(R³)(CH₃)O)_(5.4)(Si(R⁴)(CH₃)O)_(14.4)(SiO₂)In the above formula, R² is a polyether copolymers having the averageformula—CH₂CH₂CH₂(OCH₂CH₂)₈OH, R³ is a n-octyl group and R⁴ is2-phenylpropyl radical.

This laboratory prepared material is obtained from the hydrosilylationreaction between polysiloxane hydride from Example 34, 1-octene,alphamethylstyrene (AMS) and a polyether with the average formula ofCH₂═CHCH₂(OCH₂CH₂)₈OH. A nitrogen blanketed glass reactor at atmosphericpressure, which was equipped with a temperature probe, an agitator, acondenser and a nitrogen inlet, was charged with 40 g of polysiloxanehydride from Example 1. The reactor was heated to 74° C. and Karstedt'scatalyst, equivalent to 5 ppm of Platinum was dissolved in 8.6 g of AMSwas added to the reaction vessel. The reaction was exothermic and thereactor temperature rose to 100° C. within 2 minutes. The reaction wascontinued till all the AMS was consumed (as confirmed by H-NMR). Then39.6 g of allyl polyether above was charged into the reactor followed byimmediate addition of 3.1 g of 1-octene containing Karstedt's catalystequivalent to 5 ppm of Platinum to the reactor. This reaction was alsoexothermic and the temperature increased to about 110° C. The reactionmixture turned from a heterogeneous system to a homogeneous one and theheating was continued at 100° C. for another three hours until all thehydrides were consumed (as confirmed by H-NMR). The copolymer wasallowed to cool with stirring in the reactor for 30 minutes and thenremoved.

Demulsifier Efficiency Tests With Crude Oils

In the following examples tests of the new silicones structures, aloneand in combinations with each other, with organic demulsifiers and withother silicone demulsifiers will be described.

The organic demulsifiers were:

ORG A: Kemelix 3551X, a modified alkoxylate, with 100% actives,available from Croda, East Yorkshire, UK.

ORG B: Voranol CP6001, a polyether polyol, available from Dow ChemicalCo., Midland, Mich.

ORG C: Voranol EP1900, a polyether polyol, available from Dow ChemicalCo., Midland, Mich.

ORG D: Kemelix D501, an alkoxylated ethylenediamine, with 100% actives,available from Croda, East Yorkshire, UK.

ORG E: Kemelix 3422X, a polymeric alkoxylate, with 100% actives,available from Croda, East Yorkshire, UK.

ORG F: Kemelix 3515X, a polymeric alkoxylate, with 100% actives,available from Croda, East Yorkshire, UK.

ORG G: Voranol CP1421, a polyether polyol, available from Dow ChemicalCo., Midland, Mich.

ORG H: Voranol CP3040, a polyether polyol, available from Dow ChemicalCo., Midland, Mich.

ORG I: A competitive, organic demulsifier package, which is currentlyused to separate the crude oil emulsion that we studied (its compositionis unknown).

ORG J: Organic demulsifier #8619 from Baker Petrolite, Sugar Land, Tex.,USA

ORG K: Witbreak DRM-9510, an organic demulsifier, available from AkzoNobel, Netherlands.

ORG L: Kemelix 3575X, an alkoxylated phenolic resin, with 81% actives,available from Croda, East Yorkshire, UK.

ORG M: Kemelix D310, an alkoxylated phenolic resin, with 88% actives,available from Croda, East Yorkshire, UK.

ORG N: Kemelix D317, a modified polyol, available from Croda, EastYorkshire, UK.

DM046: organic demulsifier package from Baker Petrolite, Sugar Land,Tex., USA

The comparative silicone demulsifiers were:

Silbreak 400, Silbreak 401, Silbreak 402, Silbreak 323, Silbreak 329,Silbreak 603, Silbreak 638, Silbreak 1324 and Silbreak 1840 are modifiedpolydimethylsiloxanes, available from Momentive Performance materials,Wilton, Conn.

Silwet L-8610: a linear siloxane polyethylene oxide copolymer, with 1700emol molecular mass, 100% actives, available from Momentive Performancematerials, Wilton, Conn.

SIL A: a lab made epoxy-silicone polyether terpolymer, which wasring-opened with diethanol amine and had the formula(CH₃)₃SiO(Si(CH₃)₂O)₃₀₀(Si(R²)(CH₃)O)₃₀M(R³)(CH₃)O)₂₀Si(CH₃)₃,

where, R² is a mixture of two polyether copolymers having the averageformulas —CH₂CH₂CH₂(OCH₂CH₂)₁₃(OCH(CH₃)CH₂)₁₆OH and—CH₂CH₂CH₂—(OCH₂CH₂)₃₃(OCH(CH₃)CH₂)₄₂OH such that the combined averagemolecular weight is approximately 2200 g/mol; and R³ is anepoxide-containing group of the formula —(CH₂)₃OCH₂CH(O)CH₂.

SIL B: a lab made epoxy-silicone polyether terpolymer, which wasring-opened with diethanol amine and had the formula(CH₃)₃SiO(Si(CH₃)₂O)₃₀₀(Si(R²)(CH₃)O)₆(Si(R³)(CH₃)O)₄Si(CH₃)₃,

where, R² is a mixture of two polyether copolymers having the averageformulas —CH₂CH₂CH₂(OCH₂CH₂)₁₃(OCH(CH₃)CH₂)₁₆OH and—CH₂CH₂CH₂—(OCH₂CH₂)₃₃(OCH(CH₃)CH₂)₄₂OH such that the combined averagemolecular weight is approximately 2200 g/mol; and R³ is anepoxide-containing group of the formula —(CH₂)₃OCH₂CH(O)CH₂.

SIL C: a lab made epoxy-silicone polyether terpolymer, which wasring-opened with diethanol amine and had the formula(CH₃)₃SiO(Si(CH₃)₂O)₃₀₀(Si(R²)(CH₃)O)₁₅(Si(R³)(CH₃)O)₁₀Si(CH₃)₃,

where, R² is a mixture of two polyether copolymers having the averageformulas —CH₂CH₂CH₂(OCH₂CH₂)₁₃(OCH(CH₃)CH₂)₁₆OH and—CH₂CH₂CH₂—(OCH₂CH₂)₃₃(OCH(CH₃)CH₂)₄₂OH such that the combined averagemolecular weight is approximately 2200 g/mol; and R³ is anepoxide-containing group of the formula —(CH₂)₃OCH₂CH(O)CH₂.

Demulsification Tests With Crude Oil A:

Test method: The following test methods to evaluate the demulsifiers wasperformed: The standard 100 mL ASTM D4007 conical glass tubes (about 37mm diameter and 200 mm height from Imeth AG, Germany) were used for thebottle test. One hundred milliliters of crude oil was added to the tubeand the diluted demulsifier was added as a 10% solution in xylene. A fewdemulsifiers were not soluble at this concentration in xylene and werethen diluted in 2-methylpropane-1-ol. The injection was done with amicro syringe on top of the crude oil surface.

A rack of 8 conical tubes was used to perform the bottle tests. The rackwas shaken by hand for 60 seconds, at 30° angle to horizontal direction(the tubes were shaken downwards, head of tubes being down), followed by60 seconds pause used for opening the tubes for degassing and again 60seconds shaking. The volume of the separated water was recorded after adefined time for examples 36-39 with or without centrifugation of bigtubes.

The dryness of the oil phase was measured following the ASTM Test MethodD4007. After the phase separation process about 6 mL sample was takenfrom the top of the oil phase and then added to preheated toluene (60°C.) in a graduated, conical centrifuge tube (up to the 50% level). Thetubes were then strongly shaken for a few seconds. The followingparameters were recorded:

-   -   % Free water: the percentage of water separated in the graduated        tube after centrifugation (1500 RPM/5 min)    -   % Total water: the percentage of water found in the graduated        tube after adding 1-2 drops of a “knockout dropper” DM046 (from        Baker Petrolite, Sugar Land, Tex., USA), keeping the tube at        60° C. for at least 10 min and centrifugation at 1500 RPM/5 min.    -   % Interfacial emulsion: % total water minus % free water.

In some of the tests the interface quality (between the separated waterphase and the crude oil phase) was also evaluated and graded, “S”meaning Soft interface (by twisting the tube the interface moveseasily), “M” meaning Medium quality interface (by twisting the tube theinterface moves with difficulty) and “H” for Hard interface (by twistingthe tube the interface does not move at all). A “V” was added if theproperty was enhanced (meaning “Very”).

Crude oil A was from the Middle East and it was collected daily at atank after the gas-oil separator before the demulsifier injection point.(The emulsion was stable and even no free water separated the next day,confirming we have no demulsifier in the crude.)

This crude oil was from offshore, had an API of 28, a water cut of ca.18%, a low H₂S content and contained few ppm of polydimethylsiloxane(PDMS) as antifoam. The tubes we heated to 60° C. (caps opened) afteraddition of our silicones. This temperature corresponded to thedemulsification condition on the field.

One Component Demulsifiers:

In Table 1 the percentages of water separation were calculated after 15,30 and 60 minutes, using 100 ppm actives of demulsifiers, at 60° C. Fromthe comparative silicones, Silbreak 1840 showed 33% water separationafter 60 min. Silbreak 638 and Silbreak 1324 were exhibiting a very lowresidual emulsion in the top oil phase, meaning that they could be usedin formulation with other demulsifiers. ORG C led to 14% waterseparation, with a high residual emulsion (% interface) in the top oilphase. Examples 16 and 17 led to 10-11% of water separation after 1 hourwith the same type of quality of top oil phase than the ORG C. Example27 had a different behavior in the sense that it separated only 2% waterbut the top oil phase had quite a low residual emulsion and highpercentage of total water content. Examples 11 and 12 led to the driestoil phase even compared to organics, even if they showed no waterseparation after 1 hour at 60° C.

TABLE 1 Demulsification results for Crude oil A, at 60° C. and at 100ppm actives of one component demulsifier. Water separation (%) TOP OILPHASE After After After % Free % Total % Demulsifier 15 min 30 min 1 hrWater Water Interface Neat Crude 0 0 0 0 18 18 Oil A Silbreak 323 0 0 04 12 8 Silbreak 329 0 0 2 2 9.4 7.4 Silbreak 638 0 0 0 13 13 0 Silbreak1324 0 0 0 8 6 2 Silbreak 1840 17 31 33 2 9 7 Silwet L-8610 0 0 0 11 165 Silbreak 401 0 1 2 2 14.4 12.2 Silbreak 402 0 0 0 0 3.4 3.4 SIL A 0 00 0 4.2 4.2 SIL B 0 0 0 0 4.2 4.2 SIL C 0 0 0 0 2.4 2.4 ORG C 0 0 14 314 11 ORG G 0 0 0 6 18 12 ORG H 0 0 0 12 18 6 Example 27 0 0 2 16 18.82.8 DMO 46 0 0 0 3 17.7 14.7 Example 11 0 0 0 0 1 1 Example 12 0 0 0 0 11 Example 14 0 0 0 0 12 12 Example 15 0 0 0 0 9 9 Example 16 0 0 11 0 1313 Example 17 0 0 10 4 16 12 Example 18 0 0 2 6 16 10 ORG F 0 0 0 0 2.22.2

Demulsifier blends: then blends of two silicones were tested and wefound that blends containing the new silicone demulsifier structuresoutperformed the organic demulsifiers and the individual silicones.Tables 2/a and 2/b show the best blends sorted out according to thepercentage of water separated after 1 hour and after 24 h (+30 minutesat 60° C.), and according to the dryness of the top oil phase.

An evaluation of interface quality is also given in Table 2/b. All thebest candidates gave either a soft interface or a medium qualityinterface. With 4 binary blends (SIL B/Example 27 (75:25), SIL B/Example27 (50:50), SIL C/Example 27 (50:50), Example 12/Example 27 (50:50)) ofsilicones at a 100 ppm treat rate we could reach 83% of water separationafter only 1 hour (compared to 33% with only one silicone). Four-sixhours later, at room temperature, the blends Example 12 /Example 27 andExample 11/Example 27 (50:50) at 100 ppm led to up to 98% waterseparation. The blend of Silbreak 402 and Example 27 (50:50) and 100 ppmled to 83% water separation. All these blends performed better in waterseparation than ORG F/Example 27 (50:50), 100 ppm and led to atop oilphase containing less than 2% water. A reduction of the treat rate to 50ppm did not decrease too much the demulsification efficiency of some ofthese blends.

TABLE 2/a Demulsification tests with Crude oil A, at 60° C. and at 50 to100 ppm actives of demulsifier blends. Best performing systems, based onrate of water separation % Separated % Separated water after 1 h ppmwater after ppm at 60° C. + Best demulsifiers demulsifier 1 h at 60° C.Best demulsifiers demulsifier 4-6 h at 24° C. SIL B/Example 27 100 83Example 12/Example 27 100 98 (75:25) (50:50) SIL B/Example 27 100 83Example 11/Example 27 100 94 (50:50) (50:50) SIL C/Example 27 100 83 SILB/Example 27 100 89 (50:50) (75:25) Example 12/Example 27 100 83 SILC/Example 27 100 89 (50:50) (50:50) Silbreak 402/Example 27 100 78 SILB/Example 27 100 86 (50:50) (50:50) SIL B/Example 27 100 72 Silbreak402/Example 27 100 83 (25:75) (50:50) Example 11/Example 27 100 72 SILB/Example 27 100 78 (50:50) (25:75) SIL B/Example 27 50 67 SIL B/Example27 50 67 (50:50) (50:50) SIL B/Example 27 50 64 (25:75)

TABLE 2/b Demulsification tests with Crude oil A, at 60° C. and at 50 to100 ppm actives of demulsifier blends. Best performing systems, based onwater separation overnight and total residual water content in top oilphase % Separated % Total Water after Water overnight at in top ppm 24°C. + 30 min Interface Water ppm oil Best demulsifiers demulsifier at 60°C. Quality quality Best demulsifiers demulsifier phase Example12/Example 27 100 98 S Medium Example 11 100 1 (50:50) Example11/Example 27 100 97 S Medium Example 12 100 1 (50:50) SIL C/Example 27100 94 S Medium Example 11/Example 100 1.4 (50:50) 27 (50:50) SILB/Example 27 100 92 S Clear SIL B/Example 27 100 1.8 (75:25) (75:25) SILB/Example 27 100 89 S Clear Example 12/Example 100 2 (50:50) 27 (50:50)SIL B/Example 27 100 87 S Clear (25:75) Silbreak 402/Example 100 86 SMedium 27 (50:50) SIL B/Example 27 50 72 S Medium (50:50) ORG F/Example27 100 72 S Medium (50:50)

The best blends in water separation and top oil dryness were blends SILB/Example27 (75:25), Example 12/Example 27 (50:50) and Example11/Example 27 (50:50). They were much better than the single componentsof the blend (synergy) and better than a blend of an organic and asilicone like ORG F/EXAMPLE 27 (50:50) at 100 ppm.

Demulsification of Crude Oil B:

One component demulsifiers: Crude oil B was also from the Middle East.It had a higher sulfur content, API 33° and a water cut of 10%. Wetested the best pure silicones and the best blends found for crude oilA. The demulsification in bottle tests were also done at 60° C. Theresults can be found in Table 3 using 100 ppm demulsifiers.

TABLE 3 Demulsification of Crude oil B at 60° C. and 100 ppm actives ofone component demulsifiers % Water separation TOP OIL PHASE After AfterAfter % Free % Total % Interface Demulsifier 15 min 30 min 1 hr WaterWater calculated Neat Crude 0 0 0 0 10 10 Oil B Silwet 0 5 28 3.6 4.20.6 L-8610 Silbreak 402 0 25 30 0.2 1.2 1 SIL B 0 0 2 0 0.4 0.4 SIL C 7075 80 0.4 1.4 1 ORG C 0 0 0 1 1 1 Example 27 0 28 90 0.6 0.8 0.2 Example11 0 0 0 0 4.8 4.8 Example 14 0 0 0 0 2.4 2.4 Example 16 35 55 70 0 0.80.8 Example 17 70 72 80 0 1.4 1.4 ORG F 0 0 0 0 2.2 2.2 ORG A 15 35 45 44.4 0.4 Silbreak 323 60 70 70 2.2 2.4 0.2 Silbreak 603 0 70 75 1 1.2 0.2Silbreak 70 75 80 0.4 1.6 1.2 1840

For Crude oil B silicones on their own showed better water separationthan in Crude oil A. Silbreak 1840 and Silbreak 603 were efficientsilicone demulsifiers with a percentage of water of separation after 1hour up to 80%. Silbreak 1840 had a quick speed of separation in thisoil. Both are giving a quite dry top oil phase with 1.2 and 1.6% oftotal water. Example 27 was giving the best (but slowest) separationresults reaching 90% of water separation. Example 17 and Example 14 weregood candidates as they allowed 80% of water separation after 1 hour.

Demulsifier blends: Table 4 shows the results obtained for the bestblends used with crude oil A and also some new blends tested for theCrude oil B only.

TABLE 4 Demulsification of crude oil B, at 60° C., with demulsifierblends. Demulsifier % Water separation TOP OIL PHASE actives After AfterAfter % Free % Total % Demulsifier blend (ppm) 15 min 30 min 1 hr WaterWater Interface Neat Crude Oil B 0 0 0 0 0 10 10 SIL B/Example 27 100100 100 100 0 0 0 (75:25) Silbreak 402/ 100 72 80 82 1.2 1.6 0.4 Example27 (50:50) Example 11/ 100 98 100 100 0.4 0.4 0 Example 27 (50:50) ORGF/Example 27 100 90 93 95 0.2 0.4 0.2 (50:50) ORG F/Silwet L- 100 0 0 700 0.2 0.2 8610 (50:50) Silbreak 1840/ORG 100 45 55 70 0.4 1 0.6 A(75:25) Silbreak 603/ORG 100 Nd 60 70 2 2 2 A (75:25) SIL B/ORG A 100 Nd80 80 0.2 0.2 0 (75:25) SIL B/Example 18 100 Nd 90 90 0 0 0 (50:50) SILB/Example 27 100 Nd 85 88 0 0 0 (50:50) SIL B/Example 27 100 Nd 82 85 00.2 0.2 (25:75) ORG A/ORG F 100 60 70 70 0.4 0.8 0.4 (75:25) SILB/Example 27 50 75 82 85 0 0.2 0.2 (75:25) SIL B/Example 27 50 80 82 820 0.4 0.4 (50:50) Nd: not determined

Two blends SIL B/Example 27 (75:25), Example 11/Example 27 (50:50),resulted in a 100% water separation, very quickly (15-30 min) and a drytop oil phase, which was a big improvement compared to the singlecomponent demulsifiers. Other good blends were SIL B/Example 18 (50:50)and SIL B/Example 27 (50:50). A decrease of the treat rate of some goodblends decreased only slightly the performance of the blends.

Demulsification tests with Crude oil C: Crude oil C was also from theMiddle East, from off shore wells. It had an API of 29° and a water cutof 10%. The H₂S content of this crude was low. Live crude oil C wascollected daily before the gas-oil separator. The crude oil from thepipe was collected in cans and was let to degas. Temperature of thecollected crude is around 37° C. In the lab, temperature of crude goesdown and the bottle tests were run between 27 and 29° C. The results areshown in Table 5. In this Table the percentages of separation werecalculated after 30 min, after 30 min+centrifugation, and after 30min+centrifirgation+little shake to simulate the demulsificationprocess.

After centrifugation (simulating the shear in the demulsification tank)the rate of separation increased due to the presence of demulsifier. Thecentrifugation of neat crude oil led to zero water separation indicatingthat centrifugation alone does not cause separation, without the actionof demulsifier. The interface quality (between the separated water phaseand the crude oil phase) is also given in Table 5.

TABLE 5 Demulsification results for Crude oil C, API = 29° Water cut 10%at 27-29° C. with one component demulsifier Water separation (%) TOP OILPHASE Demulsifier after 30 min + % % Interface actives after after 30min + centrif. + % Free Total interfacial Quality Demulsifier (ppm) 30min centrif. little shake Water Water emulsion nd Neat Crude 0 0 0 0 01.6 1.6 Oil C M Silbreak 323 100 0 40 45 0 1.6 1.6 S Silbreak 1840 100 052 55 0 1.4 1.4 S Silwet L- 100 0 3 12 0.8 1.6 0.8 8610 S Example 27 1000 7 15 0 2.2 2.2 nd Example 11 100 0 0 0 0 1.6 1.6 nd Example 15 100 0 00 0 1.8 1.8 S Example 17 100 0 22 25 0 1.0 1.0 nd Example 18 100 0 0 0 02.4 2.4 nd ORG A 100 0 3 3 0.4 2.0 1.6 nd: not determined

Table 5 shows that Example 17 led to a better water separation (25%) anda better dryness of the oil (with 1% total water in the top of the oilphase) than ORG A. It showed also a better oil dryness than Silbreak 323and Silbreak 1840, silicone demulsifiers.

Blends of demulsifiers: blends of silicone demulsifiers were also testedto improve the water separation rate and dryness of the oil. Table 6shows various blends sorted out according to the percentage of waterseparated after “30 min+centrifugation” and “after 24 h (+30 minutes at60° C.), and according to the dryness of the top oil phase for crude oilC.

Table 6 contains the results for some of the best demulsifiers. Theblend of Example 11 and Example 27 shows best demulsification results at50:50 ratio and 100 ppm actives, corresponding to a synergy between thetwo silicones compared to the single components. At 50 ppm it stillshows good demulsifying properties, better than for the best organic ORGA at 100 ppm actives (see Table 5).

The blend of Example 27 and SIL B shows also good demulsifyingperformances compared to the single components, a synergy between a newand a comparative silicone demulsifier.

TABLE 6 Demulsification tests with the best silicone demulsifiersblends, using Crude oil C, at 27-29° C. Level Water separation (%) TOPOIL PHASE of After 30 min + % Interface actives After 30 min +Centrif. + % Free % Total Interfacial Quality Demulsifier (ppm)) After30 min Centrif. little shake Water Water emulsion Nd Neat Crude Oil CPure 0 0 0 0 1.6 1.6 Xylene S Example 11/Example 100 35 98 100 0 0.0 0.027 (50:50) S Example 11/Example 75 21 88 91 0 0.2 0.2 27 (50:50) S SILB/Example 27 100 0 90 90 0 0.4 0.4 (50:50) VS SIL B/Example27 100 0 6780 0 0.4 0.4 (25:75) S SIL B/Example 27 75 0 80 80 0 1.0 1.0 (50:50) SSIL B/Example 27 100 0 60 78 0 0.2 0.2 (75:25) H Example 11/Example 50 060 77 0 1.2 1.2 27 (50:50)

Demulsification Tests With Crude Oil D:

Crude oil D came from the middle east, from off-shore wells and had anAPI of 25° and a water cut of ca. 18%. Water separation was recorded at27-29° C. for 30 min and afterwards centrifugation of the 100 mL tubeswas performed. The centrifugation of neat crude oil led to zero waterseparation indicating that centrifugation alone does not causeseparation without the action of demulsifier.

Silicones were first tested individually to see their performance inthis crude oil. The results with 100 ppm individual, silicone andorganic demulsifiers are shown in Table 7.

Example 17 led to 74% water separation with a dryer oil than Silbreak1840 or Silbreak 323 comparative silicones. Some reproducibilityproblems occurred with this product too from one day to the next. On thesame day Example 17 led to more water separation with a drier oil otherthan the best organic, ORG D (37% water separation and 3.8% total waterin the top oil phase). With Example 17 the dryness of the top oil isless than with ORG B, which led to the driest top oil phase (close toSilbreak 1840) nevertheless with no visible water separation in thetube.

TABLE 7 Demulsification results with Crude oil D, at 27-29° C. and 100ppm treat rate with one component demulsifier. Water separated (%) After30 min + After Centrif. + TOP OIL PHASE Interface After 30 min + little% Free % Total % Interfacial Quality Demulsifier 30 min Centrif. shakeWater Water emulsion nd Neat Crude Oil D 0 1 1 0 6.0 6.0 M Silbreak 18400 40 46 0 0.8 0.8 M Silbreak 323 0 20 46 0 5.2 5.2 nd Silbreak 603 0 1 20 5.2 5.2 nd Silwet L-8610 0 3 3 0.8 4.4 3.6 nd Silbreak 402 0 0 0 0 3.03.0 nd ORG B 0 0 0 0 0.6 0.6 nd SIL B 0 1 1 0 1.9 1.9 nd SIL B 0 1 2 03.6 3.6 H SIL C 0 10 10 0 2.0 2.0 nd ORG C 0 1 1 0 4.4 4.4 nd Example 270 10 10 0.2 4.0 3.8 nd Example 11 0 0 0 0 2.4 2.4 nd Example 15 0 1 1 05.2 5.2 S Example 17 0 51 74 0 4.4 4.4 M Example 17 0 17 26 0 9.0 9.0 HExample 18 0 17 17 0 5.1 5.1 S ORG D 0 35 37 0 3.8 3.8 nd ORG E 0 3 3 02.8 2.8 nd ORG F 0 1 1 0 1.1 1.1 nd ORG A 0 2 2 0 3.2 3.2

Blends of demulsifiers: Blends of various silicones were also tested toimprove the demulsifying performance with crude oil D. Table 8 showsthat maximum 80% water separation was reached with blends of twosilicones for crude oil D and dryer oil than with one silicone only (seeTable 7). Some synergy can be shown between two silicones or with onesilicone and one organic demulsifier. The best blends in waterseparation were Example 11/Example27 (50:50) and ORG F/Example 27(50:50) which both showed better demulsification results than theindividual components alone. Blends of Example 11/Example 27 (50:50) andSIL B/ORG E (75:25) provided the driest top oil phase, which were muchdryer than with the individual components.

The blend Example 11 /Example 27 (50:50) at 100 ppm actives was the bestdemulsifying blend for both crude oil C (see Example 38) and crude oil Dat 27-29° C. and after centrifugation.

TABLE 8 Demulsification tests with Crude oil D at 27-29° C. withdemulsifier blends. Water separated (%) Level After 30 min + TOP OILPHASE of Centrif. + % Total Interface actives After After 30 min +little % Free Water % Interfacial Quality Demulsifier (ppm) 30 minCentrif. shake Water with emulsion nd Neat Crude Oil D Pure 0 1 0 0 6.06.0 xylene S Example 11/Example 27 100 0 80 80 0 1.2 1.2 (50:50) 100 ppmS Example 11/Example 27 100 1 71 77 0 0.6 0.6 (50:50) 100 ppm VS Example11/Example 27 100 0 63 69 0 0.8 0.8 (50:50) 100 ppm VS Example11/Example 27 200 0 74 80 0 0.1 0.1 (50:50) 200 ppm S ORG F/Example 27100 0 63 74 0.4 1.6 1.2 (50:50) 100 ppm nd SIL B/ORG E 100 0 0 0 0 0.60.6 (75:25)

Demulsification Efficiency Tests with Crude Oil E:

The phase separation of a sample of Crude Oil E, a heavy crude oil (API:10) containing about 36 wt. % emulsified water, from Alberta, Canada wasstudied. The total acid number of the samples was about 1.5 mg KOH/g,the asphaltene content was about 4%, the filterable solids content was660 lb/1000 bbl and the salt content was 1180 lb/1000 bbl.

Test procedure with Crude Oil E: The crude sample was homogenized byfirst heating it to about 60° C. and then thoroughly shaking thecontainer by hand for several minutes. One hundred grams of crude oilemulsion was carefully poured into prescription glass bottles, which hadmarks at 10 ml intervals (”San-Glas Ovals-Flint“, made by Owen-Brockway,Ill., USA) and threaded cap. The silicone demulsifiers were diluted to30% with xylene. First, the bottles with the crude oil sample wereheated for 5 min in an oil bath, which was at 85° C. Then the bottleswere flipped twice, followed by shaking them with a Bamstead/Labline Max2000 orbital shaker for 10 min, at 270 shakes/min rate and then placingthe bottles back to the bath at 85° C. After 1 hour heating the bottleswere shaken again with the orbital shaker for another 10 minutes andthen placed back to the bath at 85° C. After 30 minutes the bottles wereflipped ten times sideways with a rocking motion. After one hour thebottles were gently flipped, horizontally, twenty times to break up the“eggs” at the interface. After about 20-22 hours, the jars were takenout of the oil bath and the quality of the water/crude oil interface wasinspected and the volume in percent (%) of the separated water phase wasmeasured. The water content of the separated crude oil was measured withtwo methods: 1.) a small sample (0.05-0.5 ml) was taken from the middleof the crude oil phase. The water content of this small sample wasmeasured with Karl-Fischer titration using a Brinkman Titrino Workcellwith “751 GDP” titrator and Hydranal Composite-2 titrator solution; 2.)about 15 ml sample was extracted from the bottom of the oil phase with asyringe and then poured into 12.5 ml Kimble conical-bottom glasscentrifuge tubes up to the 50% mark and then diluted up to 100% withtoluene. The diluted samples were centrifuged for five minutes at 2500rpm with an IEC HN-SII centrifuge. The amount of separated water wasrecorded (“Free water”). The amount of total water was measured byadding 1-2 drops of knockout dropper (DMO46 from Baker Petrolite) andmixing the emulsion and heating it up in a water bath followed bycentrifugation as above. The “emulsion” content of the crude wascalculated by subtracting the “free water” content from the total watercontent.

Table 9 illustrates that competitive demulsification performance couldbe achieved with the new silicone compositions. For example,combinations of Organic M, Silbreak 400 and Example 10 or Example 11outperform all the organic demulsifiers tested (last six tests).

TABLE 9 Results of demulsification tests with Crude Oil H, at 85° C. %water K. Fisher, Centrifuge test, after 20-22 h ppm ppm separated andafter 20-22 h % Total % # Demulsifier as is (actives) Interface % water% Free water water Emulsion 1 Blank  0  0  6 25.85 6 34 28 2 ORG I 300150 37.1 1.55 0.51 1.44 0.93 3 ORG J 400 120 38 B* 1.77 0.60 1.70 1.10 4Example 11 400 120 36 B 2.72 1.9 1.6 −0.3 5 Example 12 400 120 36 B 2.540.6 1.6 1 6 Example 17 400 120 36 B 2.64 1.8 2 0.2 7 Example 18 400 12026 B 19.35 6 16 10 8 Example 29 400 120 29 B 8.30 2.8 4.4 1.6 9 Example30 400 120 19 B 20.53 6 18 12 10 Example 14 400 120 25 16.89 0.2 12 11.611 8619 + Example 17; 1:2 blend 133 + 267 40 + 80 30 13.50 3.2 13 9.8 128619 + Example 22, 1:1 200 + 200 60 + 60 28 B 9.13 3.6 12 8.4 13 ORG J +Example 10, 1:1 200 + 200 60 + 60 37 B 0.80 0.6 0.8 0.2 14 ORG J +Example 10, 1:1 200 + 200 60 + 60 39 BB 4.08 0.8 5.2 4.4 15 ORG J +Example 10, 1:1 200 + 200 60 + 60 32 B 8.21 1.2 8 6.8 16 ORG J + Example10, 1:1 200 + 200 40 + 80 34 B 8.75 1.6 10 8.4 17 ORG J + Example 10,1:2 133 + 267 40 + 80 34 BB 2.67 1.2 3.2 2 18 ORG J + Example 10, 1:2133 + 267 40 + 80 32 B 5.10 0.6 4.5 3.9 19 ORG J + Example 10, 1:2 267 +133 80 + 40 39 BB 2.35 0.8 2.8 2 20 ORG J + Example 11; 1:1 200 + 20060 + 60 39 B 0.77 0.4 0.9 0.5 21 ORG J + Example 11; 1:1 200 + 200 60 +60 33 B 3.96 0.8 2 1.2 22 ORG J + Example 11; 1:2 133 + 267 40 + 80 33 B7.39 0.8 3.8 3 23 ORG J + Example 11; 2:1 267 + 133 80 + 40 33 B 2.771.6 3 1.4 24 ORG J + Example 12; 1:1 200 + 200 60 + 60 35 B 2.77 0.8 2.41.6 25 ORG J + Example 12; 1:1 200 + 200 60 + 60 38 B 5.02 1.2 4.8 3.626 ORG J + Example 12; 1:2 133 + 267 40 + 80 35 B 3.25 0.2 1.4 1.2 27ORG J + Example 12; 1:2 133 + 267 40 + 80 34 B 1.81 0.4 2 1.6 28 ORG J +Example 12; 2:1 267 + 133 80 + 40 38 BB 2.45 0.8 3.4 2.6 29 ORG J +Example 12; 1:1 200 + 200 40 + 80 32 11.25 2.4 12 9.6 30 ORG J + Example22; 1:1 200 + 200 60 + 60 33 B 2.40 1.6 2.8 1.2 31 ORG J + Example 23;1:1 200 + 200 60 + 60 38 0.93 0.8 1.2 0.4 32 ORG J + Example 23; 1:1200 + 200 60 + 60 35 B 5.54 1.6 8 6.4 33 ORG J + Example 23; 1:2 133 +267 40 + 80 34 B 3.91 2.8 5 2.2 34 ORG J + Example 23; 2:1 267 + 13380 + 40 37 5.93 2 3.8 1.8 35 ORG J + Example 24; 1:1 200 + 200 60 + 6036 1.06 1.2 1.6 0.4 36 ORG K 400 120 38 2.09 0.6 2 1.4 37 ORG K +Example 12; 1:1 200 + 200 60 + 60 37 2.06 1.6 2 0.4 38 ORG K + Example12; 1:1 200 + 200 60 + 60 38 4.93 1.2 4.4 3.2 39 ORG L 400 120 36B 2.130.5 2.3 1.8 40 ORG L + Example 12; 1:1 200 + 200 60 + 60 37 5.06 1.8 4.93.1 41 ORG L + Example 12; 1:1 200 + 200 60 + 60 39 3.02 0.4 3 2.6 42ORG M 400 120 37 B 2.06 1.5 2.4 0.9 43 ORG M + Example 12; 1:1 200 + 20060 + 60 38 2.21 2 2 0 44 ORG M + Example 12; 1:1 200 + 200 60 + 60 373.15 3.2 3.8 0.6 45 ORG N 400 120 37 B 2.12 0.33 1.3 0.97 46 ORG N +Example 12; 1:1 200 + 200 60 + 60 34 4.10 0.8 3.8 3 47 ORG N + Example12; 1:1 200 + 200 60 + 60 38 3.09 0.8 2 1.2 48 Silbreak 400 400 120 346.98 3.33 6.80 3.47 49 ORG M + Silbreak 400 + 133 + 133 + 133 40 + 40 +40 38 1.13 0.8 0.8 0 Example 11, 1:1:1 50 ORG M + Silbreak 400 + 133 +133 + 133 40 + 40 + 40 38 0.91 0.4 0.8 0.4 Example 11, 1:1:1 51 ORG M +Silbreak 400 + 133 + 133 + 133 40 + 40 + 40 40 0.66 0.4 0.6 0.2 Example10, 1:1:1 52 ORG M + Silbreak 400 + 100 + 100 + 100 30 + 30 + 30 33 3.070.8 3 2.2 Example 11, 1:1:1 53 ORG M + Silbreak 400 + 100 + 100 + 10030 + 30 + 30 38 B 2.33 0.8 1.6 0.8 Example 11, 1:1:1 54 ORG M + Silbreak100 + 100 + 100 30 + 30 + 30 39 0.69 0 0 0 400 + Example 10, 1:1:1 *B:baggy interface; BB: very baggy interface

While the invention has been described with reference to a preferredembodiment, those skilled in the art will understand that variouschanges may be made and equivalents may be substituted for elementsthereof without departing from the scope of the invention. It isintended that the invention not be limited to the particular embodimentdisclosed as the best mode for carrying out this invention, but that theinvention will include all embodiments falling within the scope of theappended claims. All citations referred herein are expresslyincorporated herein by reference.

1-15. (canceled)
 16. A method for separating emulsions of oil and water,the method comprising incorporating a demulsifying-effective amount ofat least one polyorganosiloxane demulsifier into an emulsion comprisingan oil phase and an aqueous phase, the polyorganosiloxane demulsifierhaving a molecular structure comprising a polysiloxane backbone of atleast two siloxane units covalently bound to (i) one or more pendantalkylene oxide groups comprising one or more alkylene oxide unitsindependently having 1 to 6 carbon atoms, and (ii) one or more pendantgroups having the formula (C_(r)H_(2r))B wherein r equals 0 to 30 and Bis an aryl radical; and optionally (iii) one or more pendant alkylgroups having up to 40 carbon atoms.
 17. The method of claim 16, whereinthe polyorganosiloxane has the formula:M¹ _(a)M² _(b)M³ _(c)M⁴ _(d)D¹ _(e)D² _(f)D³ _(g)D⁴ _(h)T¹ _(i)T² _(j)T³_(k)T⁴ _(l)Q_(m) wherein: M¹=R¹R²R³SiO_(1/2) M²=R⁴R⁵R⁶SiO_(1/2)M³=R⁷R⁸R⁹SiO_(1/2) M⁴=R¹⁰R¹¹R¹²SiO_(1/2) D¹=R¹³R¹⁴SiO_(2/2)D²=R¹⁵R¹⁶SiO_(2/2) D³=R¹⁷R¹⁸SiO_(2/2) D⁴=R¹⁹R²⁰SiO_(2/2) T¹=R²¹SiO_(3/2)T²=R²²SiO_(3/2) T³=R²³SiO_(3/2) T⁴=R²⁴SiO_(3/2) Q=SiO_(4/2) and, R¹ isan alkyl group having from 1 to 12 carbon atoms, an OH or OR²⁵; R², R³,R⁵, R⁶, R⁸, R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are alkyl groups having from 1to 12 carbon atoms; R⁴, R¹⁵, R²² are(C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶, n equals 0 to6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, providedo+p+q≧1; R⁷, R¹⁷, R²³ are branched, linear or cyclic, saturated orunsaturated alkyl groups having from 4 to 36 carbon atoms; R¹⁰, R¹⁹, R²⁴are aryl groups having the general formula (C_(r)H_(2r))B wherein requals 0-30 and B is an aryl radical; R¹¹, R¹², R²⁰ are aryl groupshaving the general formula (C_(r)H_(2r))B, wherein r equals 0 to 30 oran alkyl group having from 1 to 12 carbon atoms; R²⁵is an alkyl groupwith 1 to 12 carbon atoms and R²⁶ is a hydrogen or an alkyl groupshaving from 1 to 12 carbon atoms , wherein the subscripts a, b, c, d, e,f, g, h, i, j, k, l, m are zero or positive integers for moleculessubject to the following limitations: 3≦a+b+c+d+e+f+g+h+i+j+k+l+m≦500,b+f+j≧1, c+g+k≧0, d+h+l≧1, and (a+b+c+d) equals 2+i+j+k+1+2m.
 18. Themethod of claim 17, wherein R¹ is CH₃, OH or OCH₃; R², R³, R⁵, R⁶, R⁸,R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are CH₃, R²⁰ is an aryl having the formula(C_(r)H_(2r))B and R¹¹, R¹² are either CH₃ or an aryl having the formula(C_(r)H_(2r))B, with the proviso if the polysiloxane contains diphenylR¹⁹ and R²⁰ are C₆H₅.
 19. The method of claim 17, wherein R¹ is CH₃, OHor OCH₃; R², R³, R⁵, R⁶, R⁸, R⁹, R¹³, R¹⁴, R¹⁶, R¹⁸, R²¹ are CH₃, andR¹¹, R¹², R²⁰ are CH₃.
 20. The method of claim 16, wherein thepolyorganosiloxane has the formula:M¹ _(a)M² _(b)M³ _(c)M⁴ _(d)D¹ _(e)D² _(f)D³ _(g)D⁴ _(h) wherein:M¹=R¹R²R³SiO_(1/2) M²=R⁴R⁵R⁶SiO_(1/2) M³=R⁷R⁸R⁹SiO_(1/2)M⁴=R¹⁰R¹¹R¹²SiO_(1/2) D¹=R¹³R¹⁴SiO_(2/2) D²=R¹⁵R¹⁴SiO_(2/2)D³=R¹⁷R¹⁸SiO_(2/2) D⁴=R¹⁹R²⁰SiO_(2/2) and, R¹ is an alkyl group havingfrom 1 to 12 carbon atoms, an OH or OR²⁵; R², R³, R⁵, R⁶, R⁸, R⁹, R¹³,R¹⁴, R¹⁶, R¹⁸ are alkyl groups having from 1 to 12 carbon atoms; R⁴, andR¹⁵, are (C_(n)H_(2n))—O—(C₂H₄O)_(p)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶; nequals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to50, provided o+p+q≧1; R⁷ and R¹⁷ are linear, branched or cyclic,saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms;R¹⁰ and R¹⁹ are aryl groups having the general formula (C_(r)H_(2r))Bwherein r equals 0-30 and B is an aryl radical; R¹¹, R¹², R²⁰ are arylgroups having the general formula (C_(r)H_(2r))B, wherein r equals 0 to30 or an alkyl group having from 1 to 12 carbon atoms; R²⁵ is an alkylgroup with 1 to 12 carbon atoms and R²⁶ is a hydrogen or an alkyl groupshaving from 1 to 12 carbon atoms, 3≦a+b+c+d+e+f+g+h≦500, b+f≧1, c+g≧0,d+h≧1, and a plus b plus c plus d equals
 2. 21. The method of claim 16,wherein polyorganosiloxane has the formula:M¹ _(a)D¹ _(c)D² _(f)D³ _(g)D⁴ _(h)T¹ _(i)T² _(j)T³ _(k)T₄ _(l)Q_(m)wherein M¹=R¹R²R³SiO_(1/2) D¹=R¹³R¹⁴SiO_(2/2) D²=R¹⁵R¹⁶SiO_(2/2)D³=R¹⁷R¹⁸SiO_(2/2) D⁴=R¹⁹R²⁰SiO_(2/2) T¹=R²¹SiO_(3/2) T²=R²²SiO_(3/2)T³=R²³SiO_(3/2) T⁴=R²⁴SiO_(3/2) Q=SiO_(4/2) and, R¹ is an alkyl grouphaving from 1 to 12 carbon atoms, an OH or OR²⁵; R², R³, R¹³, R¹⁴, R¹⁶,R¹⁸, R²¹ are alkyl groups having from 1 to 12 carbon atoms; R¹⁵, R²² are(C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶, n equals 0 to6, o equals 0 to 100, p equals 0 to 50, provided o+p+q≧1; R¹⁷ and R²³are linear, branched or cyclic, saturated or unsaturated alkyl groupshaving from 4 to 36 carbon atoms; R¹⁹ and R²⁴ are aryl groups having thegeneral formula (C_(r)H_(2r))B wherein r equals 0-30 and B is an arylradical; R²° is an aryl group having the general formula (C_(r)H_(2r))B,wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbonatoms; R²⁵ is an alkyl group with 1 to 12 carbon atoms and R²⁶ is ahydrogen or an alkyl groups having from 1 to 12 carbon atoms,i+j+k+l+m>0; a=2+i+j+k+l+2m , 3≦a+e+f+g+h+i+j+k+l+m≦500, f+j≧1, g+k≧0,h+l>1.
 22. The method of claim 16, wherein the polyorganosiloxane hasthe formula:M¹ D¹ _(e)D² _(f)D³ _(g)D⁴ _(h)M¹ _(a) wherein M¹=R¹R²R³SiO_(1/2)D¹=R¹³R¹⁴SiO_(2/2) D²=R¹⁵R¹⁶SiO_(2/2) D³=R¹⁷R¹⁸SiO_(2/2)D⁴=R¹⁹R²⁰SiO_(2/2) and, R¹ is an alkyl group having from 1 to 12 carbonatoms, an OH or OR²⁵; R², R³, R¹³, R¹⁴, R¹⁶, R¹⁸ are alkyl groups havingfrom 1 to 12 carbon atoms; R¹⁵ is(C_(n)H_(2n))—O—(C₂H₄O)_(o)—(C₃H₆O)_(p)—(C₄H₈O)_(q)—R²⁶, n equals 0 to6, o equals 0 to 100, p equals 0 to 100and q equals0 to 50, providedo+p+q≧1; R¹⁷ is a linear, branched or cyclic, saturated or unsaturatedalkyl groups having from 4 to 36 carbon atoms; and R¹⁹ is an aryl grouphaving the general formula (C_(r)H_(2r))B wherein r equals 0-30 and B isan aryl radical; R²° is an aryl group having the general formula(C_(r)H_(2r))B, wherein r equal 0 to 30 or an alkyl group having from 1to 12 carbon atoms; R²⁵ is an alkyl group with 1 to 12 carbon atoms andR²⁶ is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms,1≦e+f+g+h≧498, f≧1, g≧0 and h≧1.
 23. The method of claim 22, wherein R¹is CH₃, OH or OCH₃; R², R³, R¹³, R¹⁴, R¹⁶, R¹⁸ are CH₃, R²⁰ is an arylhaving the formula (C_(r)H_(2r))B, with the proviso if thepolyorganosiloxane contains diphenyl R¹⁹ and R²⁰ are C₆H₅.
 24. Themethod of claim 22, wherein R¹ is CH₃, OH or OCH₃; R², R³, R¹³, R¹⁴,R¹⁶, R¹⁸ are CH₃; and R²⁰ is CH₃.
 25. The method of claim 16, whereinthe polyorganosiloxane has the structure:

wherein X equals 0 to 498 L equals 1 to 300, K equals 0 to 300, J equals1 to 300, M equals 0 to 100 N equals 0 to 100 and O equals 2 to 33 and Zis a hydrogen or an alkyl group having from 1 to 12 carbon atoms. 26.The method of claim 16, further comprising at least one organicdemulsifier selected from the group consisting of sulfonic acids,carboxylic acids, thiocarboxylic acids, carboxylic acid esters,phosphinic acids, alkyleneoxide polymers, alkyleneoxide copolymers,alkyleneoxide-functionalized phenolic resins, epoxy resins, aminealkyleneoxides, polyimine alkoxylates, polyester amines, cationicsurfactants, bis-amides, and silicone-based polymers and silicone-basedcopolymers.
 27. The method of claim 16, wherein the at least onepolyorganosiloxane demulsifier is used at a concentration of from 0.1 to10,000 ppm of the total composition.
 28. The method of claim 16, whereinthe at least one polyorganosiloxane demulsifier is used at aconcentration of from 0.5 to 1000 ppm of the total composition.
 29. Themethod of claim 16, wherein the at least one polyorganosiloxanedemulsifier is used at a concentration of from 5 to 500 ppm of the totalcomposition.
 30. The method of claim 16, wherein the at least onepolyorganosiloxane demulsifier comprises a blend, a solution, adispersion, an oil-in-water, a water-in-oil emulsion, a microemulsion orcombinations thereof.